Process for olefin polymerization

ABSTRACT

Novel chromium-containing compounds are prepared by forming a mixture of a chromium salt, a metal amide, and an ether. These novel chromium-containing, or chromium pyrrolide, compounds, with a metal alkyl and an unsaturated hydrocarbon, can be used as a cocatalyst system in the presence of an olefin polymerization catalyst system to produce a comonomer in-situ. The resultant polymer, although produced from predominately one monomer, has characteristics of a copolymer.

This application is a division of application Ser. No. 08/109,855, filedAug. 20, 1993, now U.S. Pat. No. 5,451,645, the entirety of which isherein incorporated by reference; which is a continuation of applicationSer. No. 07/807,309, filed Dec. 13, 1991, now abandoned, the entirety ofwhich is herein incorporated by reference; which is ncontinuation-in-part of application Ser. No. 07/698,631, filed May 10,1991, now abandoned, the entirety of which is herein incorporated byreference; which is a continuation-in-part of Ser. No. 07/393,354, filedAug. 10, 1989, now abandoned, the entirety of which is hereinincorporated by reference.

BACKGROUND OF THE INVENTION

This invention relates to the polymerization of olefins, such asethylene, in the presence of any polymerization catalyst and one or morenovel chromium cocatalyst systems.

It is well known that olefins, such as ethylene, can be polymerized withcatalyst systems employing supported, chromium catalyst ormagnesium/titanium catalysts. Initially such catalysts were usedprimarily to form olefin homopolymers. It soon developed, however, thatmany applications required polymers which were more impact resistantthan olefin homopolymers. Consequently, in order to produce polymerhaving short chain branching like the more flexible free radicalpolymerized olefin polymers, comonomers such as propylene, butene,hexene or other higher olefins were copolymerized with the olefinmonomer to provide resins tailored to specific end uses. The copolymers,however, are more expensive to produce since inventories of differentmonomers must be kept and also the comonomers are generally moreexpensive than the usual short-chain monomers, such as ethylene orpropylene. Linear olefin polymers, such as polyethylene, with shortchain branching can be formed from a pure ethylene feed using the oldfree radical high pressure process, but the conditions necessary to dothis make the product too expensive to be commercially competitive.

Additional control over the polymerization process and the resultantpolymer is also desired. A process to consistently reduce the density oflinear olefin polymers and to more efficiently produce and incorporatecomonomers into the linear olefin polymer is economically advantageous.A shift in the polymer branch distribution, wherein the branch length isdecreased and the amount of branching is increased, is also economicallydesirable.

SUMMARY OF THE INVENTION

Accordingly it is an object of this invention to provide a low costroute to linear olefin polymers having toughness imparted by short chainbranching.

It is a further object of this invention to provide a process by whicholefin polymers having the properties associated with copolymers can beobtained from a pure, single olefin feed.

It is yet a further object of this invention to provide an improvedpolymerization process.

It is a further object of this invention to provide a novelpolymerization process to control polymer density.

It is yet a further object of this invention to provide a novelpolymerization process to improve comonomer production and incorporationinto olefin polymers.

It is a further object of this invention to provide a novelpolymerization process to shift olefin distribution.

It is a further object of this invention to provide a novelpolymerization process to control polymer short chain branching.

In accordance with this invention, an essentially pure, single olefinfeed is contacted under polymerization conditions with a polymerizationcatalyst and an olefin trimerization and/or oligomerization cocatalystsystem comprising the reaction product of a chromium salt, a metalamide, and an ether; an activating compound selected from the groupconsisting of metal alkyls, Lewis acids, and mixtures thereof; and anunsaturated hydrocarbon. In accordance with a second embodiment of thisinvention, an essentially pure, single olefin feed is contacted underpolymerization conditions with a polymerization catalyst and an olefintrimerization and/or oligomerization cocatalyst system comprising thereaction product of a chromium source, a pyrrole-containing compound, ametal alkyl, and an unsaturated hydrocarbon. Additionally, hydrogen canbe introduced into the polymerization reactor in an amount sufficient toaccelerate the trimerization, oligomerization and/or polymerizationprocesses.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a computer generated ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a simplified structural representation or formula, of amolecule of Product I, Cr₅ (NC₄ H₄)₁₀ (OC₄ H₈)₄, as determined by singlecrystal x-ray crystallography, and

FIG. 2 is a further simplified ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a structural representation, of the same molecule shownin FIG. 1.

FIG. 3 is a computer generated ORTEP drawing of the structure, or asimplified structural representation or formula, of a molecule ofProduct III, Cr(NC₄ H₄)₄ !⁻², as determined by single crystal x-raycrystallography.

FIG. 4 is a further simplified ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a structural representation, of the same molecule shownin FIG. 3, however, the entire crystal structure or lattice, with theformula Cr(NC₄ H₄)₄ Na₂.20C₄ H₈ is shown.

FIG. 5 is a computer generated ORTEP drawing of the structure, or asimplified structural representation or formula, of a molecule ofProduct IV, Cr(NC₄ H₄)₅ (OC₄ H₈)!⁻², as determined by single crystalx-ray crystallography, and

FIG. 6 is a further simplified ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a structural representation, of the same molecule shownin FIG. 5, however the entire crystal structure or lattice, with theformula Cr(NC₄ H₄)₅ (OC₄ H₈)! Na!₂.4(OC₄ H₈), is shown.

FIG. 7 is a computer generated ORTEP drawing of a molecule of Product V,Cr(NC₄ H₄)₃ Cl(O₂ C₂ H₄ (CH₃)₂)₃ Na, which includes the entire crystalstructure or lattice, as determined by single crystal x-raycrystallography.

FIG. 8 is a further simplified ball and stick projection of the samemolecule shown in FIG. 7.

FIG. 9 is a further simplified ball and stick projection of (Cr(NC₄ H₄)₃Cl(O₂ C₂ H₄ (CH₃)₂)!₃₁ 1, with the exception of the chromium atom whichis represented as a thermal ellipsoid. This is the same molecule as thatshown in FIGS. 7 and 8, however, the entire crystal structure, orlattice, is not shown in FIG. 9.

DETAILED DESCRIPTION OF THE INVENTION Polymerization Catalyst

The novel trimerization and/or oligomerization cocatalyst systems,including the inventive chromium compounds, can be used either supportedor unsupported as a cocatalyst with any other olefin polymerizationcatalyst. Generally, polymerization catalysts systems are consideredeither chromium catalysts (also known as "Phillips Catalysts") ortitanium, zirconium and/or vanadium-containing catalysts.

Any chromium catalyst system known in the art can be used. Commerciallyavailable chromium catalyst systems typically comprise chromium, atleast a portion of which is in the hexavalent state, supported on aninorganic oxide; optionally, the polymerization catalyst system canfurther comprise a metal alkyl co-catalyst. Exemplary chromium catalystsystems include, but are not limited to those disclosed in U.S. Pat.Nos. 3,87,494; 3,900,457; 4,053,436; 4,151,122; 4,294,724; 4,392,990;and 4,405,501, herein incorporated by reference.

Any titanium, zirconium and/or vanadium-containing catalyst system knownin the art can also be used. Commercially available titanium, zirconiumand/or vanadium catalyst systems typically comprise complexes oftransition metal halides with organometallic compounds. Exemplarymagnesium/titanium catalysts include, but are not limited to, thosedisclosed in U.S. Pat. No. 4,394,291; 4,326,988; and 4,347,158, hereinincorporated by reference.

The amount of novel trimerization and/or oligomerization cocatalystsystems, including the inventive chromium compounds used as a cocatalystcan be any amount sufficient to generate a comonomer that can beincorporated into the polymer product.

Chromium Compounds

The inventive chromium compounds, which can be used preferably forolefin trimerization and, optionally, olefin oligomerization and/orpolymerization, can be produced by forming a reaction mixture comprisinga chromium salt, a metal amide, and any electron pair donor solvent,such as, for example, an ether. As used in this disclosure, theinventive chromium compounds are referred to by a variety ofinterchangeable names, such as inventive or novel chromium compound(s),chromium complex(es), chromium pyrrole complex(es) and/or chromiumpyrrolide(s).

The chromium salt can be one or more organic or inorganic chromiumsalts, wherein the chromium oxidation state is from 0 to 6. As used inthis disclosure, chromium metal is included in this definition of achromium salt. Generally, the chromium salt will have a formula ofCrX_(n), wherein X can be the same or different and can be any organicor inorganic radical, and n is an integer from 1 to 6. Exemplary organicradicals can have from about 1 to about 20 carbon atoms per radical, andare selected from the group consisting of alkyl, alkoxy, ester, ketone,and/or amido radicals. The organic radicals can be straight-chained orbranched, cyclic or acyclic, aromatic or aliphatic, and can be made ofmixed aliphatic, aromatic, and/or cycloaliphatic groups. Exemplaryinorganic radicals include, but are not limited to halides, sulfates,and/or oxides.

Preferably, the chromium salt is a halide, such as, for example chromousfluoride, chromic fluoride, chromous chloride, chromic chloride,chromous bromide, chromic bromide, chromous iodide, chromic iodide, andmixtures thereof. Most preferably, the chromium salt is a chloride, suchas, for example chromous chloride and/or chromic chloride, due to simpleseparation of the reaction by-products such as, for example, sodiumchloride, as well as relatively low cost.

The metal amide can be any metal amide that will react with a chromiumsalt to form a chromium-amido complex. Broadly, the metal amide can beany heteroleptic or homoleptic metal complex or salt, wherein the amideradical can be any nitrogen-containing organic radical. The metal amidecan be either affirmatively added to the reaction, or generated in-situ.Generally, the metal amide will have from about 1 to about 20 carbonatoms. Exemplary metal amides include, but are not limited to, primaryand/or secondary amines, any alkali metal (Group IA, and includinghydrogen, of the Periodic Table) amide and/or any alkaline earth metal(Group IIA of the Periodic Table) amide. The hydrocarbyl portion of thesalt of the metal amide is selected from the group consisting ofstraight chain or branched, cyclic or acyclic, aromatic or aliphatic,and mixtures of two or more thereof. Preferably, the metal amide isselected from a Group IA metal, and including hydrogen, or Group IIAmetal amide, due to ease of reaction with chromium halides.

Exemplary preferred metal amides include, but are not limited to,lithium dimethylamide, lithium diethylamide, lithium diisopropylamide,lithium dicyclohexylamide, sodium bis(trimethylsilyl)amide, sodiumindolide, sodium pyrrolide, and mixtures of two or more thereof. Mostpreferably, the metal amide is a pyrrolide. As used in this disclosure,a pyrrolide is defined as a compound comprising a 5-membered,nitrogen-containing heterocycle, such as, for example, pyrrole,derivatives of pyrrole, and mixtures thereof. Exemplary pyrrolides areselected from the group consisting of hydrogen pyrrolide (pyrrole),lithium pyrrolide, sodium pyrrolide, potassium pyrrolide, cesiumpyrrolide, and/or the salts of substituted pyrrolides, because of highreactivity and activity with the other reactants. Examples of salts ofsubstituted pyrrolides include, but are not limited to sodium2,5-dimethyl pyrrolide and/or 3,4-dimethyl pyrrolide. When the metalamide is a pyrrolide ligand, the resultant chromium compound is achromium pyrrolide.

The electron pair donor solvent can be any electron pair donor solventto effect a reaction between the chromium salt and the metal amide.While not wishing to be bound by theory, it is believed that theelectron pair donor solvent can be a reaction solvent, as well as apossible reactant. Exemplary electron pair donor solvents include, butare not limited to, nitrogen-containing compounds; oxygen-containingcompounds, such as, for example, ethers; phosphorous-containingcompounds; and/or sulfur-containing compounds.

Exemplary nitrogen-containing compounds include, but are not limited tonitrites, such as, for example, acetonitrile; amines, such as, forexample, pyridine, and/or derivatives of pyridine; and/or amides.Additional exemplary nitrogen-containing compounds include, but are notlimited to, nitromethane, dimethylpyridine, dimethylformamide,N-methylformamide, aniline, nitrobenzene, tetramethyldiaminomethane,hexamethyldisilazane, and/or pyrrolidone.

Exemplary oxygen-containing compounds include, but are not limited to,acetone, ethyl acetate, methyl acetate, methanol, ethanol, ethyl methylketone, acetaldehyde, furan, and/or hexamethyldisiloxane.

Exemplary phosphorous-containing compounds include, but are not limitedto, hexamethylphosphoramide, hexamethylphosphorous triamide,triethylphosphite, tributylphosphine oxide, and/or triethylphosphine.

Exemplary sulfur-containing compounds include, but are not limited to,carbon disulfide, dimethylsulfoxide, tetramethylene sulfone, thiophene,and/or dimethylsulfide or mixtures thereof.

The ether in the reaction mixture can be one or more ether compounds toaffect a reaction between the chromium salt and the metal amide. Whilenot wishing to be bound by theory, it is believed that the ether can bea reaction solvent, as well as a possible reactant. The ether can be anyaliphatic and/or aromatic compound containing an R--O--R functionality,wherein the R groups can be the same or different, but preferably is nothydrogen. Preferred ethers are aliphatic ethers, for safety reasons inthat aromatic ethers are human toxins. Furthermore, the preferred ethersare those which facilitate a reaction between a chromium halide and aGroup IA or Group IIA metal pyrrolide, and also can be easily removedfrom the reaction mixture. Exemplary compounds include, but are notlimited to, tetrahydrofuran, dioxane, diethylether, dimethoxyethane(glyme), diglyme, triglyme, and mixtures of two or more thereof. Mostpreferably, the ether is selected from the group consisting oftetrahydrofuran, derivatives of tetrahydrofuran, dimethoxyethane,derivatives of dimethoxyethane, and mixtures thereof, for the reasonsgiven above, as well as the reason that the preferred salt of an amineis soluble in these ethers.

The amount of each reactant used to prepare one or more of the novelchromium compounds can vary, based on the desired chromium compoundproduct. Any amount of each reactant can be used to produce the novelchromium compounds, depending on the desired product. Different reactionstoichiometries can produce different chromium compounds. For example,the reaction of about one mole of chromium (II) with about two moles ofsodium pyrrolide can produce different products than reacting about onemole of chromium (II) with an excess of sodium pyrrolide. Furthermore,as stated earlier, selection of different, although similar reactants,can produce different products. For example, using eithertetrahydrofuran or dimethoxyethane can result in a different reactionproduct.

The three reactants can be combined in any manner under conditionssuitable to form a solution comprising one or more of the inventivechromium compounds. The reaction preferably occurs in the absence ofoxygen and moisture and therefore under an inert atmosphere, such as,for example nitrogen and/or argon. The reaction pressure can be anypressure sufficient to maintain the reactants in a liquid state.Generally, pressure within the range of from about atmospheric pressureto about three atmospheres are acceptable. For ease of operationatmospheric pressure is generally employed.

The reaction temperature can be any temperature which maintains theether in a liquid form. In order to effectuate a more efficientreaction, temperatures near the boiling point of the ether arepreferred. Most preferably, the reaction temperature is at the boilingpoint of the ether and the reaction mixture is refluxed for a period oftime.

The reaction time can be any amount of time necessary for the reactionto occur. Depending on the reactants, as well as the reactiontemperature and pressure, reaction time can vary from about 1 minute toabout 1 week. Usually, reaction time ranges from about 3 hours to about5 days. Under optimum conditions, the reaction time can be within therange of from about 3 to about 48 hours.

After the reaction is complete, a solid reaction product can berecovered by any method known in the art. Preferably, though notrequired, upon completion of the reaction, the reaction mixture first isfiltered to remove any particulate reaction by-products such as, forexample, salts, like sodium chloride, prior to any other treatment.Although removal of any reaction by-products is not necessary, suchremoval preferably is done in order to expedite later purification ofthe chromium product. After filtering, one exemplary method to recover asolid reaction product is to remove the excess ether from the reactionmixture. The excess electron pair donor solvent, such as, for example anether, can be removed according to any method known in the art.Exemplary electron pair donor solvent, such as, for example an ether,removal methods include, but are not limited to, slow evaporation, undervacuum and/or a nitrogen purge.

Other electron pair donor solvents, such as, for example, an ether,removal procedures can be used either alone or in combination. Forexample, the reaction mixture can be filtered and then vacuum dried.Preferably, the reaction mixture is heated slowly and maintained at atemperature within the range of about 10° to about 300° C., preferablyabout 25° to about 200° C., under a vacuum, for safety, to remove theexcess electron pair donor solvent, such as, for example an ether. Theresultant solid reaction product is one or more of the inventivechromium compounds.

Alternatively, the reaction mixture can be filtered to remove any solidreaction by-product solids and the filtered reaction mixture can becontacted with a non-polar organic solvent. Addition of a non-polarorganic solvent causes one or more of the inventive chromium compoundsto form a solid precipitate. Exemplary non-polar organic solventsinclude, but are not limited to, pentane, hexane, cyclohexane, heptane,and mixtures thereof. Most preferably pentane is added to the filteredreaction mixture because of the availability and ease of use.

The precipitated inventive chromium compounds can be recovered by anymethod known in the art. The simplest procedure to remove the inventiveprecipitated chromium compounds is by filtration.

The reaction mixture and the resultant solid reaction products, asstated earlier, are kept in an oxygen-free atmosphere at all times.Preferably, due to availability and ease of use, an inert atmospheresuch as, for example, nitrogen, is the ambient.

Numerous chromium compounds can be prepared in accordance to theinvention, by varying the reactants and/or the quantity of each reactantemployed. The recovered, novel chromium compound or compounds can beused for olefin trimerization and/or polymerization without furtherpurification.

Optionally, the chromium compound can be purified in accordance with anymethod known in the art. For example, one of the simplest purificationprocedures is to wash the recovered solid with a non-polar organicsolvent such as, for example, toluene. Preferably, a non-polar aliphaticorganic solvent is used for best results. Exemplary wash solventsinclude, but are not limited to, pentane, hexane, cyclohexane, heptane,and mixtures thereof. Most preferably, pentane is the wash solvent.

Novel metal pyrrolides can also be prepared from salts of other metals.Exemplary metals include, but are not limited to, nickel, cobalt, iron,molybdenum, and copper. As with the previously described chromium salt,the metal oxidation state of the metal can be any oxidation state,including the elemental, or metallic, state. These novel metalpyrrolides can be prepared in a manner similar to the previouslydescribed chromium pyrrolides.

Catalyst Systems

Catalyst systems prepared in accordance with this invention can be usedpreferably for olefin trimerization and, optionally, olefinoligomerization and/or polymerization. Catalyst systems comprise a metalsource, a pyrrole-containing compound, a metal alkyl, also called anactivating compound, and an unsaturated hydrocarbon compound. Exemplarymetal sources are selected from the group consisting of chromium,nickel, cobalt, iron, molybdenum, and copper. While this disclosuredeals primarily with chromium salts and chromium sources, other metalsources, which can result in less active catalyst systems, can besubstituted for the chromium salt or chromium source. Preferably,catalyst systems comprise a chromium source, a pyrrole-containingcompound, a metal alkyl, also called an activating compound, and anunsaturated hydrocarbon compound for best resultant catalyst systemactivity and product selectivity. Optionally, for ease of use, achromium pyrrolide can provide both the chromium source and thepyrrole-containing compound. As used in this disclosure, when a chromiumpyrrolide is used to form a catalyst system, a chromium pyrrolide isconsidered to provide both the chromium source and thepyrrole-containing compound. Catalyst systems can further comprise acatalyst support.

In accordance with one embodiment of the invention, the inventivechromium compounds can be combined in a reaction mixture with a metalalkyl and an unsaturated hydrocarbon compound and can be used, either asa supported and/or unsupported catalyst system, for olefintrimerization, oligomerization and/or polymerization. The novel chromiumcompounds provide a chromium source, as well as a pyrrole-containingcompound, for catalyst systems prepared in accordance with this firstembodiment.

A supported chromium catalyst system can be prepared with any supportuseful to support a chromium catalyst. Exemplary catalyst supportsinclude, but are not limited to, zeolites inorganic oxides, either aloneor in combination, phosphated inorganic oxides, and mixtures thereof.Particularly preferred are supports selected from the group consistingof silica, silica-alumina, alumina, fluorided alumina, silated alumina,thoria, aluminophosphate, aluminum phosphate, phosphated silica,phosphated alumina, silica-titania, coprecipitated silica/titania,fluorided/silated alumina, and mixtures, thereof, being presentlypreferred, as well as any one or more of these supports which cancontain chromium. The presently most preferred catalyst support, becauseof the greatest trimerization activity, is aluminophosphate, asdisclosed in U.S. Pat. No. 4,364,855 (1982), herein incorporated byreference.

Supported chromium catalyst systems can be prepared according to anymethod known in the art. For example, the inventive chromium compoundreaction mixture, which preferably has been filtered to remove anyparticulate reaction by-products and contains one or more of the novelchromium pyrrolide compounds, is combined and thoroughly contacted witha catalyst support. Excess electron pair donor solvent, such as, forexample an ether, does not have to be removed prior to contacting thecatalyst support. However, a solid chromium pyrrolide compound can bere-dissolved in an electron pair donor solvent, such as, for example anether, if desired. The chromium pyrrolide/electron pair donor, such as,for example, an ether solution is usually a blue or blue/green color,although other colors can be observed.

The catalyst support usually is insoluble in the electron pair donorsolvent, such as, for example, an ether/chromium pyrrolide complexsolution. Any excess of the chromium pyrrolide in relation to thecatalyst support is sufficient. However, usually, less than about 5grams of chromium pyrrolide compound per gram of catalyst support issufficient. Preferably, about 0.001 to about 1 gram of chromiumpyrrolide compound per gram of support, and most preferably, 0.01 to 0.5gram of chromium pyrrolide compound per gram of support is used for bestsupport loading and most efficient use of the reagents. The amount ofchromium pyrrolide compound per gram of support can be expressed indifferent, yet equivalent terms, such as, for example, moles of chromiumper gram of support. Usually, less than about 8.6×10⁻³ moles of chromiumper gram of support is sufficient. Preferably, about 1.7×10⁻⁶ to about1.7×10⁻⁵ to 8.6×10⁻⁴ moles of chromium per gram of support are used, forreasons given above.

This mixture can be contacted and mixed at any time, temperature, andpressure to thoroughly contact the chromium pyrrolide compound andsupport. For ease of use, ambient temperatures and pressures arepreferred. Mixing times can be up to about 24 hours, preferably, lessthan about 10 hours, and most preferably, from 1 second to 8 hours.Longer times usually provide no additional benefit and shorter times canbe insufficient for thorough contacting.

After the support is added and thoroughly combined with the chromiumpyrrolide, it can be collected by filtration, vacuum dried, then anactivating compound, usually as a solution of one or more Lewis acidsand/or metal alkyls, preferably in an unsaturated hydrocarbon compoundsolvent, is added to the support/chromium pyrrolide mixture. An active,supported catalyst system then can be collected by filtration. As usedin this disclosure, a Lewis acid is defined as any compound that is anelectron acceptor. Preferably, the activating compound is a compoundthat can be considered both a Lewis acid and a metal alkyl. Theactivating compound can have any number of carbon atoms. However, due tocommercial availability and ease of use, the activating compound willusually comprise less than about 70 carbon atoms per metal alkylmolecule and preferably less than about 20 carbon atoms per molecule.Preferred activating compounds which are both a metal alkyl and a Lewisacid include, but are not limited to, alkylaluminum compounds,alkylboron compounds, alkylmagnesium, alkylzinc, and/or alkyllithiumcompounds. Exemplary metal alkyls include, but are not limited to,n-butyllithium, s-butyllithium, t-butyllithium, diethylmagnesium,dibutylmagnesium, diethylzinc, triethylaluminum, trimethylaluminum,triisobutylaluminum, and mixtures thereof. Most preferably, activatingcompounds are selected from the group consisting of non-hydrolyzed,i.e., not pre-contacted with water, alkylaluminum compounds, derivativesof alkylaluminum compounds, halogenated alkylaluminum compounds, andmixtures thereof for improved product selectivity, as well as improvedcatalyst system reactivity, activity, and/or productivity. Exemplarycompounds include, but are not limited to, triethylaluminum,tripropylaluminum, tributylaluminum, diethylaluminum chloride,diethylaluminum bromide, diethylaluminum ethoxide, ethylaluminumsesquichloride, and mixtures thereof for best catalyst system activityand product selectivity. The most preferred alkylaluminum compound istriethylaluminum, for best results in catalyst system activity andproduct selectivity.

When a trimerization catalyst system is the desired product, theactivating compound must be a non-hydrolyzed alkylaluminum compound,expressed by the general formulae AlR₃, AlR₂ X, AlRX₂, AlR₂ OR, AlRXOR,and/or Al₂ R₂ X₃, wherein R is an alkyl group and X is a halogen atom.Exemplary compounds include, but are not limited to, triethylaluminum,tripropylaluminum, tributylaluminum, diethylaluminumchloride,diethylaluminumbromide, diethylaluminumethoxide, diethylaluminumphenoxide, ethylaluminumethoxychloride, and/or ethylaluminumsesquichloride. Preferably, the activating compound for a trimerizationcatalyst system is a trialkylaluminum compound, AlR₃, for reasons givenabove. The most preferred trialkylaluminum compound is triethylaluminum,for reasons given above.

Any amount of activating compound, such as a metal alkyl and/or a Lewisacid, is sufficient to activate and/or react with the chromium pyrrolidecatalyst. Usually about 200 grams of activating compound, i.e., metalalkyl and/or a Lewis acid, per gram of chromium can be used. Preferably,about 1 to about 100 grams of activating compound, such as a metal alkyland/or a Lewis acid, per gram of chromium pyrrolide, and most preferablyabout 5 to about 30 grams of activating compound, such as a metal alkyland/or a Lewis acid, per gram of chromium pyrrolide are used, for bestcatalyst activity. However, the amount of activating compound, such as ametal alkyl and/or a Lewis acid employed can vary with the catalystsupport used. For example, if the support is silica and/or alumina, toomuch activating compound, such as a metal alkyl and/or a Lewis acid candecrease catalyst activity. However, a similar amount of activatingcompound, such as a metal alkyl and/or a Lewis acid, used with analuminophosphate support does not always significantly decrease catalystactivity.

The unsaturated hydrocarbon compound, also referred to in thisapplication as a solvent compound, can be any combination of one or morearomatic or aliphatic unsaturated hydrocarbon compounds. While notwishing to be bound by theory, it is believed that an unsaturatedhydrocarbon compound acts as more than a solvent, and can be a reactantand/or a stabilizing component during and/or subsequent to formation ofan inventive catalyst system. Exemplary unsaturated hydrocarboncompounds, such as, for example, a solvent, can be any unsaturatedhydrocarbon compound that can dissolve the activating compound, i.e.,whereinthe activating compound can be a Lewis acid and/or metal alkyl.Preferred unsaturated hydrocarbon compounds include, but are not limitedto, unsaturated hydrocarbons comprising less than about 70 carbon atomsper molecule, aromatic compounds having from about 6 to about 50 carbonatoms per molecule and preferably unsaturated hydrocarbons comprisingless than about 20 carbon atoms per molecule, due to commercialavailability and ease of use. Specific exemplary unsaturated aliphaticcompounds include, but are not limited to, ethylene, 1-hexene,1,3-butadiene, and mixtures thereof. The most preferred unsaturatedaliphatic hydrocarbon compound is ethylene because of elimination ofcatalyst system preparation steps and ethylene can be a trimerizationand/or oligomerization reactant. Specific exemplary unsaturated aromatichydrocarbon compounds include, but are not limited to, toluene, benzene,xylene, mesitylene, hexamethylbenzene, and mixtures thereof. Mostpreferably, the unsaturated aromatic hydrocarbon compound solvent istoluene, for ease of removal and minimal interference with the resultantcatalyst system, as well as increased trimerization and/oroligomerization activity.

The unsaturated hydrocarbon compound can be present either during theinitial contacting of a chromium pyrrolide and activating compound,i.e., prior to introduction into a trimerization, oligomerization and/orpolymerization reactor, or the unsaturated hydrocarbon compound can beintroduced directly into the reactor. Furthermore, one or more of theolefin reactants can be considered the unsaturated hydrocarbon.Preferably, the unsaturated hydrocarbon is present during the initialcontacting of a chromium pyrrolide and activating compound in order tostabilize the resultant catalyst system. In the absence of anunsaturated hydrocarbon, the resultant catalyst system can deactivateand lose activity over a period of time.

While any amount of unsaturated hydrocarbon compound can be used, toomuch or too little can adversely affect catalyst system activity.Therefore, preferably, the resultant catalyst system is stripped of anyexcess unsaturated aromatic hydrocarbon. Stripping of excess unsaturatedaromatic hydrocarbon can be accomplished by any method known in the art,such as, for example, solvent removal methods. Exemplary removal methodsinclude, but are not limited to, filtration, vacuum drying, drying underan inert atmosphere, and combinations thereof. While not wishing to bebound by theory, it is believed that the remaining unsaturatedhydrocarbon can stabilize the resultant catalyst system. If nounsaturated hydrocarbon is present, it is believed that the catalystsystem can lose activity.

As disclosed earlier, the mixture of supported chromium pyrrolide,activating compound, such as a metal alkyl and/or a Lewis acid, andunsaturated hydrocarbon are mixed and/or contacted under a dry, inertatmosphere at all times. Any pressure can be used during the contacting;for ease of use, atmospheric pressure is preferred. Any temperature canbe used during the contacting; for ease of use, room temperature, orambient temperature, is preferred. Some care should be taken during themixing, so as not to destroy the physical integrity of the chromiumpyrrolide, catalyst support, and resultant supported catalyst. Thefour-component mixture can be contacted for any amount of timesufficient to prepare and activate a chromium catalyst system. Usually,times in the range of about one minute to about one week are sufficient.Preferably, times in the range of about 30 minutes to about 24 hours areused, and most preferably times in the range of about one hour to about12 hours are used. Too short of mixing times can result in incompletecontacting and too long of mixing times will not provide any additionalcatalytic benefit. An active, supported catalyst system then can becollected by filtration.

An alternative, and presently preferred, method to produce a supportedcatalyst system is to combine one or more solid, inventive chromiumpyrrolide compounds with an unsaturated hydrocarbon solvent, asdisclosed earlier, such as, for example, toluene and/or ethylene, and anactivating compound, as disclosed earlier, such as a metal alkyl and/ora Lewis acid, such as, for example, triethylaluminum. This mixture canbe stirred for any time sufficient to dissolve the chromium pyrrolidecompound, at any pressure or temperature. Usually, times of about oneminute to about one week, preferably about one hour to about 24 hours,and most preferably within the range of about three hours to about 12hours are used. For ease of operation, ambient temperatures andpressures are used. Usually, a brown solution will result.

After the solution is sufficiently mixed, a support is added to thesolution and stirred to thoroughly contact the solution and support. Thequantity of support added is any amount sufficient to support thechromium pyrrolide compound. Generally, the amount of support necessaryis the same as that disclosed in the previous exemplary process. Anysuitable pressure and temperature can be used, although ambienttemperature and pressure are preferred for ease of use. Usually, themixing and/or contacting time is within the range of about 30 minutes toabout one week, preferably from about 3 hours to about 48 hours. Mostpreferably, the mixing and/or contacting time is within the range ofabout 5 hours to about 24 hours, to maximize efficiency and result in athoroughly contacted support. Alternatively, the support can be addedconcurrently with an inventive chromium compound, an aluminum alkyl, andan unsaturated hydrocarbon.

The solution then can be filtered to recover a solid catalytic product.The catalytic product, as with the reactants and reactions, ispreferably kept under a dry, inert atmosphere to maintain chemicalstability.

If an inventive chromium compound, such as, for example, a chromiumpyrrolide, is recovered, i.e., isolated, it can be used as anunsupported trimerization, oligomerization and/or polymerizationcatalyst. Olefins can be trimerized, oligomerized and/or polymerized ina presence of one or more of these inventive chromium compounds, anunsaturated hydrocarbon and an activating compound, such as, for examplea Lewis acid and/or a metal alkyl.

In accordance with a second embodiment of the invention, a catalystsystem can be prepared by forming a reaction mixture comprising achromium source, a pyrrole-containing compound, a metal alkyl and anunsaturated hydrocarbon compound. These catalyst systems can furthercomprise a catalyst support. A chromium pyrrolide can be used as both achromium source and a pyrrole-containing compound.

The chromium source, similar to the earlier discussed chromium salt, canbe one or more organic or inorganic chromium compounds, wherein thechromium oxidation state is from 0 to 6. As used in this disclosure,chromium metal is included in this definition of a chromium salt.Generally, the chromium source will have a formula of CrX_(n), wherein Xcan be the same or different and can be any organic or inorganicradical, and n is an integer from 1 to 6. Exemplary organic radicals canhave from about 1 to about 20 carbon atoms per radical, and are selectedfrom the group consisting of alkyl, alkoxy, ester, ketone, and/or amidoradicals. The organic radicals can be straight-chained or branched,cyclic or acyclic, aromatic or aliphatic, can can be made of mixedaliphatic, aromatic, and/or cycloaliphatic groups. Exemplary inorganicradicals include, but are not limited to halides, sulfates, and/oroxides.

Preferably, the chromium source is a chromium(II)- and/orchromium(III)-containing compound which can yield a catalyst system withimproved trimerization activity. Most preferably, the chromium source isa chromium(III) compound because of ease of use, availability, andenhanced catalyst system activity. Exemplary chromium(III) compoundsinclude, but are not limited to, chromium carboxylates, chromiumnaphthenates, chromium halides, chromium pyrrolides, and/or chromiumdionates. Specific exemplary chromium(III) compounds include, but arenot limited to, chromium(III)2,2,6,6-tetramethylheptanedionate Cr(TMHD)₃!, chromium(III)2-ethylhexanoate Cr(EH)₃ !, chromium(III)naphthenateCr(Np)₃, chromium(III) chloride, chromium (III) tris(2-ethylhexanoate),chromic bromide, chromic chloride, chromic fluoride, chromium (III)oxy-2-ethylhexanoate, chromium (III) dichloroethylhexanoate, chromium(III) acetylacetonate, chromium (III) acetate, chromium (III) butyrate,chromium (III) neopentanoate, chromium (III) laurate, chromium (III)stearate, chromium (III) pyrrolides, and/or chromium (III) oxalate.

Specific exemplary chromium (II) compounds include, but are not limitedto, chromous fluoride, chromous chloride, chromous bromide, chromousiodide, chromium (II) bis(2-ethylhexanoate), chromium (II) acetate,chromium (II) butyrate, chromium (II) neopentanoate, chromium (II)laurate, chromium (II) stearate, chromium (II) pyrrolides, and/orchromium (II) oxalate.

The pyrrole-containing compound can be any pyrrole-containing compoundthat will react with a chromium salt to form a chromium pyrrolidecomplex. As used in this disclosure, the term "pyrrole-containingcompound" refers to hydrogen pyrrolide, i.e., pyrrole, (C₄ H₅ N),derivatives of hydrogen pyrrolide, as well as metal pyrrolide complexes.A "pyrrolide", as discussed earlier is defined as a compound comprisinga 5-membered, nitrogen-containing heterocycle, such as, for example,pyrrole, derivatives of pyrrole, and mixtures thereof. Broadly, thepyrrole-containing compound can be pyrrole and/or any heteroleptic orhomoleptic metal complex or salt, containing a pyrrolide radical, orligand. The pyrrole-containing compound can be either affirmativelyadded to the reaction, or generated in-situ. Generally, thepyrrole-containing compound will have from about 1 to about 20 carbonatoms per molecule. Exemplary pyrrolides are selected from the groupconsisting of hydrogen pyrrolide (pyrrole), derivatives of pyrrole,substituted pyrrolides, lithium pyrrolide, sodium pyrrolide, potassiumpyrrolide, cesium pyrrolide, and/or the salts of substituted pyrrolides,because of high reactivity and activity with the other reactants.Examples of substituted pyrrolides include, but are not limited topyrrole-2-carboxylic acid, 2-acetylpyrrole, pyrrole-2-carboxaldehyde,tetrahydroindole, 2,5-dimethyl-pyrrole, 2,4-dimethyl-3-ethylpyrrole,3-acetyl-2,4-dimethylpyrrole,ethyl-2,4-dimethyl-5-(ethoxycarbonyl)-3-pyrrole-propionate,ethyl-3,5-dimethyl-2-pyrrole-carboxylate. When the pyrrole-containingcompound contains chromium, the resultant chromium compound can becalled a chromium pyrrolide.

The most preferred pyrrole-containing compounds used in a trimerizationcatalyst system are selected from the group consisting of hydrogenpyrrolide, i.e., pyrrole (C₄ H₅ N) and/or 2,5-dimethyl pyrrole. Whileall pyrrole-containing compounds can produce catalysts with highactivity and productivity, use of pyrrole and/or 2,5-dimethylpyrrole canproduce a catalyst system with enhanced activity and selectivity to adesired trimerized product, such as, for example, the trimerization ofethylene to 1-hexene, as well as decreased polymer production.

The metal alkyl, also referred to earlier as an activating compound, canbe any heteroleptic or homoleptic metal alkyl compound. One or moremetal alkyls can be used. The ligand(s) on the metal can be aliphaticand/or aromatic. Preferably, the ligand(s) are any saturated orunsaturated aliphatic radical. The metal alkyl can have any number ofcarbon atoms. However, due to commercial availability and ease of use,the metal alkyl will usually comprise less than about 70 carbon atomsper metal alkyl molecule and preferably less than about 20 carbon atomsper molecule. Preferred metal alkyls include, but are not limited to,alkylaluminum compounds, alkylboron compounds, alkylmagnesium compounds,alkylzinc compounds and/or alkyllithium compounds. Exemplary metalalkyls include, but are not limited to, n-butyllithium, s-butylithium,t-butyllithium, diethylmagnesium, diethylzinc, triethylaluminum,trimethylaluminum, triisobutylaluminum, and mixtures thereof.

Most preferably, activating compounds are selected from the groupconsisting of non-hydrolyzed, i.e., not pre-contacted with water,alkylaluminum compounds, derivatives of alkylaluminum compounds,halogenated alkylaluminum compounds, and mixtures thereof for improvedproduct selectivity, as well as improved catalyst system reactivity,activity, and/or productivity. Exemplary compounds include, but are notlimited to, triethylaluminum, tripropylaluminum, tributylaluminum,diethylaluminum chloride, diethylaluminum bromide, diethylaluminumethoxide, ethylaluminum sesquichloride, and mixtures thereof for bestcatalyst system activity and product selectivity. The most preferredalkylaluminum compound is triethylaluminum, for best results in catalystsystem activity and product selectivity, as well as commercialavailability.

When a trimerization catalyst system is the desired product, theactivating compound must be at least one non-hydrolyzed alkylaluminumcompound, expressed by the general formulae AlR₃, AlR₂ X, AlRX₂, AlR₂OR, AlRXOR, and/or A1₂ R₃ X3, wherein R is an alkyl group and X is ahalogen atom. Exemplary compounds include, but are not limited to,triethylaluminum, tripropylaluminum, tributylaluminum,diethylaluminumchloride, diethylaluminumbromide,diethylaluminumethoxide, diethylaluminum phenoxide,ethylaluminumethoxy-chloride, and/or ethylaluminum sesquichloride,Preferably, the activating compound for a trimerization catalyst systemis a trialkylaluminum compound, AlR₃, for reasons given above. The mostpreferred trialkylaluminum compound is triethylaluminum, for reasonsgiven above.

Formation of stable and active catalyst systems can take place in thepresence of a unsaturated hydrocarbon. As discussed in the previousembodiment, an unsaturated hydrocarbon can be present either during theinitial contacting of a chromium source, a pyrrole-containing compoundand a metal alkyl, or can be introduced directly into a trimerization,oligomerization and/or polymerization reactor. Furthermore, one or moreof the olefin reactants can be considered the unsaturated hydrocarbon.

Any unsaturated aromatic or aliphatic hydrocarbon can be used.Preferably, an unsaturated hydrocarbon initially is present in thereaction mixture and most preferably, an aromatic hydrocarbon and/orethylene initially is present to produce a highly active catalyst interms of activity and selectivity, as well as a stable catalyst system.The unsaturated hydrocarbon can have any number of carbon atoms permolecule. Usually, the unsaturated hydrocarbon will comprise less thanabout 70 carbon atoms per molecule, preferably less than about 20 carbonatoms per molecule, due to commercial availability and ease of use.

The unsaturated hydrocarbon can be a gas, liquid, or solid. Preferably,to effect thorough contacting and mixing of the chromium salt,pyrrole-containing compound, and metal alkyl, the unsaturatedhydrocarbon will be in a liquid and/or dissolved state. Exemplaryunsaturated aliphatic hydrocarbons include, but are not limited to,ethylene, 1-hexene, 1,3-butadiene, and mixtures thereof. The mostpreferred unsaturated aliphatic hydrocarbon is ethylene, since ethylenecan be a reactant during trimerization, oligomerization, and/orpolymerization. Exemplary unsaturated aromatic hydrocarbons include, butare not limited to, toluene, benzene, xylene, mesitylene,hexamethylbenzene, and mixtures thereof. Unsaturated aromatichydrocarbons are preferred in order to improve catalyst systemstability, as well as improve catalyst system activity. The mostpreferred unsaturated aromatic hydrocarbon is toluene, for bestresultant catalyst system stability and activity.

If an unsaturated aromatic hydrocarbon is added prior to introduction ofthe chromium compound(s) to a trimerization, oligomerization and/orpolymerization reactor, removal of, or stripping, the unsaturatedaromatic hydrocarbon prior to introduction of the chromium compound(s)into a reactor can improve catalyst system activity and/or productselectivity. Removal of the unsaturated aromatic hydrocarbon can be donein any manner known in the art, such as, for example, flashing orevaporation. The resultant product is a concentrated, or saturated,solution of an inventive catalyst system.

When the unsaturated aromatic hydrocarbon is removed prior tointroduction to a reactor, the concentrated, or saturated, solution ofan inventive catalyst system can be dissolved in a solvent compatiblewith the trimerization, oligomerization and/or polymerization process toimprove ease of handling the inventive catalyst system. Generally, thesolvent is the same as the reactor diluent. Preferred solvents include,but are not limited to cyclohexane, isobutane, hexane, pentane, andmixtures thereof.

The reaction, optionally, also can take place in the presence of ahalide source. The presence of a halide source in the reaction mixturecan increase catalyst system activity and productivity, as well asincrease product selectivity. Exemplary halides include, but are notlimited to fluoride, chloride, bromide, and/or iodide. Due to ease ofuse and availability, chloride is the preferred halide. Based onimproved activity, productivity, and/or selectivity, bromide is the mostpreferred halide.

The halide source can be any compound containing a halogen. Exemplarycompounds include, but are not limited to compounds with a generalformula of R_(m) X_(n), wherein R can be any organic and/or inorganicradical, X can be a halide, selected from the group consisting offluoride, chloride, bromide, and/or iodide, and m+n can be any numbergreater than 0. If R is an organic radical, preferably R has from about1 to about 70 carbon atoms per radical, most preferably from 1 to 20carbon atoms per radical, for best compatibility and catalyst systemactivity. If R is an inorganic radical, preferably R is selected fromthe group consisting of aluminum, silicon, germanium, hydrogen, boron,lithium, tin, gallium, indium, lead, and mixtures thereof. Specificexemplary compounds include, but are not limited to, methylene chloride,chloroform, benzylchloride, silicon tetrachloride, tin (II) chloride,tin (IV) chloride, germanium tetrachloride, boron trichloride, aluminumtribromide, aluminum trichloride, 1,4-di-bromobutane, and/or1-bromobutane.

Furthermore, the chromium source, the metal alkyl and/or unsaturatedhydrocarbon can contain and provide a halide to the reaction mixture.Preferably, the halide source is an alkylaluminum halide and is used inconjunction with alkylaluminum compounds due to ease of use andcompatibility, as well as improved catalyst system activity and productselectivity. Exemplary alkylaluminum halides include, but are notlimited to, diisobutylaluminum chloride, diethylaluminum chloride,ethylaluminum sesquichloride, ethylaluminum dichioride, diethylaluminumbromide, diethylaluminum iodide, and mixtures thereof.

When a trimerization catalyst system is the desired product, preferably,the reaction mixture comprises a halide source. Furthermore, mostpreferably, the halide source is selected from the group consisting oftin (IV) halides, germanium halides, and mixtures thereof. The halidesource, most preferably, is combined with the chromium source andpyrrole-containing compound prior to addition of a metal alkyl, i.e.,the chromium source and pyrrole-containing compound are pre-treated witha halide source, to increase catalyst system productivity.

The amount of each reactant used to prepare a trimerization catalystsystem can be any amount sufficient that, when combined with one or moreolefins, trimerization, as defined in this disclosure, occurs. Usually,to prepare a trimerization catalyst system, about one mole of chromium,as the element chromium (Cr), can be combined with about 1 to about 50moles of pyrrole-containing compound and about 1 to about 75 moles ofaluminum, as the element, in an excess of unsaturated hydrocarbon. If anoptional halide source is present, usually about 1 to about 75 moles ofhalide, as the element, are present. Preferably, about 1 mole ofchromium, calculated as the element chromium (Cr), can be combined withabout 1 to about 15 moles of pyrrole-containing compound and about 5 toabout 40 moles of aluminum, calculated as the element aluminum (Al), inan excess of unsaturated hydrocarbon. If an optional halide source ispresent, preferably about 1 to about 30 moles of halide, calculated aselemental halide (X), are present. Most preferably, about one mole ofchromium, as the element (Cr), is combined with two to four moles ofpyrrole-containing compound and 10 to 20 moles of aluminum, as theelement (Al), in an excess of unsaturated hydrocarbon. If an optionalhalide source is present, most preferably 2 to 15 moles of halide, as anelement (X), are present.

An excess of pyrrole-containing compound does not appear to improvecatalyst system activity, productivity, and/or selectivity. Anunsaturated hydrocarbon can improve catalyst system stability, activity,and/or selectivity. An excess of the unsaturated hydrocarbon can harmcatalyst system selectivity and/or acitvity. Too much alkylaluminum candecrease catalyst system activity and product selectivity. Too littlealkylaluminum can result in incomplete formation of a catalyst system,which in turn, can result in low catalyst system activity and increaseformation of undesired polymeric by-products. An excess of an optionalhalide source can deactivate a catalyst system, and therefore can resultin decreased catalyst system activity. As stated earlier, presence of ahalide source can increase catalyst system activity and productselectivity.

The reactants can be combined in any manner under conditions suitable toform an effective catalyst system. While the reactants can be combinedin any manner, preferably the pyrrole-containing compound is present inthe reaction mixture prior to the introduction of the metal alkyl. Ifthis order of addition is followed, a better catalyst system, in termsof product selectivity and catalyst system activity and productivity,can be produced.

The reaction preferably occurs in the absence of oxygen, which candeactivate the catalyst, and under anhydrous conditions, i.e., in theinitial absence of water. Therefore a dry, inert atmosphere, such as,for example, nitrogen and/or argon is most preferred. Additionally, themetal alkyl is a non-hydrolyzed metal alkyl.

The reaction pressure can be any pressure which does not adverselyeffect the reaction. Generally, pressures within the range of from aboutatmospheric pressure to about three atmospheres are acceptable. For easeof operation atmospheric pressure is generally employed.

The reaction temperature can be any temperature. In order to effectuatea more efficient reaction, temperatures which maintain the reactionmixture in a liquid state, for reasons given above, are preferred.

The reaction time can be any amount of time necessary for the reactionto occur. The reaction can be considered a dissolution process; anyamount of time which can dissolve substantially all reactants issufficient. Depending on the reactants, as well as the reactiontemperature and pressure, reaction time can vary. Usually, times of lessthan about 1 day can be sufficient. Usually, reaction time is less thanabout 60 minutes. Under optimum conditions, the reaction time can bewithin the range of from about 1 second to about 15 minutes. Longertimes usually provide no additional benefit and shorter times may notallow sufficient time for complete reaction.

In accordance with the second embodiment of preparation, aheterogenerous, i.e., supported, catalyst system can be prepared in-situin the reactor by adding solid support directly to the reactor. Asstated earlier, exemplary catalyst supports include, but are not limitedto, zeolites, inorganic oxides, either alone or in combination,phospbated inorganic oxides, and mixtures thereof. Particularlypreferred are supports selected from the group consisting of silica,silica-alumina, alumina, fluorided alumina, silated alumina, thoria,aluminophosphate, aluminum phosphate, phosphated silica, phosphatedalumina, silica-titania, coprecipitated silica/titania,fluorided/silated alumina, and mixtures, thereof, being presentlypreferred, as well as any one or more of these supports which cancontain chromium. The presently most preferred catalyst support, becauseof the greatest trimerization activity, is aluminophosphate, asdisclosed in U.S. Pat. No. 4,364,855 (1982), herein incorporated byreference. In-situ preparation of a heterogeneous catalyst system, usedin a trimerization or oligomerization process, can decrease undesirableformation of polymer.

Hetergeneous trimerization, oligomerization, and/or polymerizationcatalyst systems can also be prepared in accordance with the secondembodiment of the invention by forming a reaction mixture comprising achromium source, a pyrrole-containing compound, a metal alkyl, anunsaturated hydrocarbon, and an inorganic oxide, as disclosed earlier.Optionally, as disclosed earlier, a halide source an be added. Reactionstoichiometries and reaction conditions are the same as those disclosedfor the second embodiment of the invention.

Any excess of chromium source, in relation to the inorganic oxidecatalyst support, is sufficient. However, usually, less than about 5grams of chromium pyrrolide compound per gram of catalyst support issufficient. Preferably, about 0.001 to about 1 gram of chromiumpyrrolide compound per gram of support, and most preferably, 0.01 to 0.5gram of chromium pyrrolide compound, or chromium source, per gram ofsupport is used for best support loading and most efficient use of thereagents. The amount of chromium pyrrolide, or chromium source, compoundper gram of supprt can be expressed in different, yet equivalent terms,such as, for example, moles of chromium per gram of support. Usually,less than about 8.6×10⁻³ moles of chromium per gram of support issufficient. Preferably, about 1.7×10⁻⁶ to about 1.7×10⁻⁵ to 8.6×10⁻⁴moles of chromium per gram of support are used, for reasons given above.

The resultant heterogeneous catalyst system can be collected byfiltration, to recover a solid catalyst system product. The solidcatalyst system is preferably kept under a dry, inert atmosphere tomaintain chemical stability and reactivity.

Reactants

Reactants applicable for use in polymerization with the catalyst systemsand processes of this invention are olefinic compounds which canpolymerize, i.e., react the same or with other olefinic compounds.Catalyst systems of the invention can be used to polymerize at least onelinear or branched mono-1-olefin having about 2 to about 8 carbon atoms.Exemplary compounds include, but are not limited to, ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and mixturesthereof.

Reactants applicable for use in oligomerization processes with catalystsystems and processes of this invention are olefin compounds having fromabout 2 to about 30 carbon atoms per molecule and having at least oneolefinic double bond. Exemplary mono-olefin compounds include, but arenot limited to acyclic and cyclic olefins such as, for example,ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene,2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene,3-heptene, the four normal octenes, the four normal nonenes, andmixtures of any two or more thereof. Exemplary diolefin compoundsinclude, but are not limited to, 1,3-butadiene, isoprene,1,4-pentadiene, and 1,5-hexadiene. If branched and/or cyclic olefins areused as reactants, while not wishing to be bound by theory, it isbelieved that steric hindrance could hinder the trimerization process.Therefore, the branched and/or cyclic portion(s) of the olefinpreferably should be distant from the carbon-carbon double bond.

Trimerization, as used in this disclosure, is defined as the combinationof any two, three, or more olefins, wherein the number of olefin, i.e.,double, bonds is reduced by two. Reactants applicable for use in thetrimerization process of this invention are olefinic compounds which cana) self-react, i.e., trimerize, to give useful products such as, forexample, the self reaction of ethylene can give one hexene and theself-reaction of 1,3-butadiene can give 1,5-cyclooctadiene; and/or b)olefinic compounds which can react with other olefinic compounds, i.e.,co-trimerize, to give useful products such as, for example,co-trimerization of ethylene plus hexene can give one decene and/or1-tetradecene, co-trimerization of ethylene and 1-butene gives oneoctene, co-trimerization of 1-decene and ethylene can give 1-tetradeceneand/or 1-docosene, or co-trimerization of 1,3-butadiene and1,5-hexadiene can give 1,5-cyclo-octadecadiene. For example, the numberof olefin bonds in the combination of three ethylene units is reduced bytwo, to one olefin bond, in 1-hexene. In another example, the number ofolefin bonds in the combination of two 1,3-butadiene units, is reducedby two, to two olefin bonds in 1,5-cyclooctadiene. As used herein, theterm "trimerization" is intended to include dimerization of diolefins,as well as "co-trimerization", both as defined above.

Suitable trimerizable olefin compounds are those compounds having fromabout 2 to about 30 carbon atoms per molecule and having at least oneolefinic double bond. Exemplary mono-olefin compounds include, but arenot limited to acyclic and cyclic olefins such as, for example,ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene,2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene,3-heptene, the four normal octenes, the four normal nonenes, andmixtures of any two or more thereof. Exemplary diolefin compoundsinclude, but are not limited to, 1,3-butadiene, 1,4-pentadiene, and1,5-hexadiene. If branched and/or cyclic olefins are used as reactants,while not wishing to be bound by theory, it is believed that sterichindrance could hinder the trimerization process. Therefore, thebranched and/or cyclic portion(s) of the olefin preferably should bedistant from the carbon-carbon double bond.

Catalyst systems produced from a chromium source, a pyrrole-containingcompound, a metal alkyl and an unsaturated hydrocarbon preferably areemployed as a trimerization catalyst system, which can be used as acocatalyst system with any other polymerization catalyst system.Optionally, as stated earlier, trimerization catalyst systems can beproduced from a chromium pyrrolide (instead of a chromium source and apyrrole containing compound), a metal alkyl and an unsaturatedhydrocarbon.

Reaction Conditions

The reaction products, i.e., polymers and/or copolymers, can be preparedfrom the catalyst systems of this invention by solution reactions,slurry reactions, and/or gas phase reaction techniques usingconventional equipment and contacting processes. Contacting of themonomer or monomers with the two catalyst systems, i.e., polymerizationcatalyst system and trimerization/oligomerization cocatalyst system, canbe effected by any manner known in the art of homogeneous (liquid) orheterogeneous (solid) catalyst systems. One convenient method is tosuspend a polymerization catalyst system in an organic medium and toagitate the mixture to maintain the polymerization catalyst system insuspension throughout the trimerization and/or polymerization process.An inventive cocatalyst system can then be added. A polymerizationcatalyst system and inventive cocatalyst system, preferably, can also befed simultaneously to a polymerization reactor, via one or more catalystand/or cocatalyst system feed streams. Other known contacting methodssuch as fluidized bed, gravitating bed, and fixed bed can also beemployed.

Optionally, hydrogen can be added to the reactor to accelerate thereaction and/or increase catalyst system activity.

The catalyst systems of this invention are particularly suitable for usein trimerization and/or polymerizations. The slurry process is generallycarried out in an inert diluent (medium), such as a paraffin,cycloparaffin, or aromatic hydrocarbon. Exemplary reactor diluentsinclude, but are not limited to isobutane and cyclohexane. Isobutane candecrease the swelling of the polymer product. However, a homogeneoustrimerization/oligomerization cocatalyst system is more soluble incyclohexane. Therefore, a preferred diluent for a homogeneoustrimerization or oligomerization process is cyclohexane and a preferreddiluent for a heterogeneous trimerization or oliromeriztaion process isisobutane. When the reactant is predominately ethylene, a temperature inthe range of about 0° to about 300° C. generally can be used.Preferably, when the reactant is predominately ethylene, a temperaturein the range of about 60° to about 150° C. is employed.

Any amount of polymerization catalyst system and cocatalyst system canbe present in a polymerization reactor, in order to produce a polymerwith a desired set of optimal properties, such as, for example, density,melt index, high load melt index and molecular weight. Usually, up toabout 40 parts by weight of a supported, i.e., heterogeneous, cocatalystsystem can be present for each part by weight of polymerization catalystsystem. Preferably, about 1 to about 25 parts cocatalyst system for eachpart polymerization catalyst system, and most preferably, 3 to 15 partsby weight cocatalyst system for each part polymerization catalyst systemare present, to produce a polymer with desirable physical and processingcharacteristics.

Products

The olefinic and/or polymeric products of this invention haveestablished utility in a wide variety of application such as, forexample, as monomers for use in the preparation of homopolymers,copolymers, and/or terpolymers. The polymeric products of this inventionhave established utility in a wide variety of application such as forexample, polyethylene.

The further understanding of the present invention and its advantageswill be provided by reference to the following examples.

EXAMPLES

Various, equivalent abbreviations are used throughout the disclosure andexamples. Some of these include triethylaluminum as TEA, Al(C₂ H₅)₃ ;diethylaluminum chloride as DEAC, (Al(C₂ H₅)₂ Cl); chromium (III)2-ethylhexanoate as Cr(EH)₃, CrEH, CrEH₃ ; hydrogen pyrrolide aspyrrole, Py, PyH, (C₄ H₅ N); chromium (III) acetylacetonate as Cracac₃,Cr(acac)₃, Cr(acac), Cracac, Cr(C₅ H₇ O₂)₃ ; chromium (III) pyrrolide asCrPy₃, Cr(Py)₃, (Na(C₄ H₁₀ O₂)₂ ! Cr(C₄ H₄ N)₃ Cl(C₄ H₁₀ O₂)!, Na(DME)₂! Cr(C₄ H₄ N)₃ Cl(DME)!, Na(DME)₂ ! Cr(Py)₃ Cl(DME)!, Product V,Compound V; chromium (III) chloride tris-tetrahydrofuran as CrCl₃ THF₃,CrCl₃ (THF)₃ ; 2,5-dimethylpyrrole as hydrogen 2,5-dimethylpyrrolide, C₆H₈ N, 2,5-DMP; butene as C₄ ═; 1-hexene as 1-C₆ ═; hexene as C₆ ; octeneas c₈ ═; decene as C₁₀ ═; dodecene as C₁₂ ═; and tetradecene as C₁₄ ═.

Preparation of Chromium-Containing Compounds

Manipulations of all reactants were carried out either in a dryboxemploying nitrogen, or in airless glassware employing vacuum ornitrogen. Tetrahydrofuran (THF), toluene, benzene, diethylbenzene(Aldrich, 97% mixture of 1,2-, 1,3-, 1,4-isomers) and pentane werepurified by distillation over sodium-benzophenone ketyl under nitrogen,then degassed via a nitrogen purge. Dimethoxyethane (DME) (Aldrich,anhydrous) was degassed via nitrogen purge and used without furtherpurification. Pyrrole (Aldrich, 98%) was vacuum distilled over sodium,then degassed via nitrogen purge. 2,5-Dimethylpyrrole was dried withcalcium sulfate and vacuum distilled. Sodium 2,5-dimethylpyrrolide (NaC₆H₅ N) was prepared by reacting 2,5-dimethylpyrrole with an excess ofsodium (40% by weight dispersion in mineral spirits) in refluxingtetrahydrofuran under nitrogen. Sodium pyrrolide was prepared byreacting pyrrole with an equivalent molar amount (1:1) of NaH (Aldrich,60% by weight in mineral oil) or sodium (40% dispersion by weight inmineral spirits) in dimethoxyethane or tetrahydrofuran (THF) at ambienttemperature under nitrogen. Triethylaluminum (TEA) (Aldrich 1.0M,hexanes and 1.9M toluene) was used as received. Ketjen Grade B alumina(Al₂ O₃) and Davison 952 silica (SiO₂) were the commercial materialsused as supports for catalyst preparations. Fluorided-alumina (F/Al₂ O₃,15 wt % F) was prepared by the addition of a solution of NH₄ HF₂ inmethanol to Ketjen Grade B alumina. Phosphated silica (P/SiO₂, P/Simolar ratio=0.1) was prepared by the addition of a 10% H₃ PO₄ /methanolsolution to Davison 952 silica. The aluminophosphate (AlPO₄) used in thefollowing experiments was made as described in McDaniel et al, U.S. Pat.No. 4,364,855 (1982). The supports were activated by placing up to 25 ginto a fritted quartz tube, fluidizing with air and calcining at 700°C., except for P/SiO₂ at 350° C., for 3 hours. The air stream wasswitched to nitrogen until the support cooled to ambient temperature.

Chromium pyrrolide complexes were typically prepared from anhydrouschromium (II or III) chloride and sodium pyrrolide as follows:

A typical synthetic procedure useful to prepare chromium pyrrolidecomplexes was that of reacting the chromium chlorides with sodiumpyrrolide (NaC₄ H₄ N, also referred to as NaPy) in refluxingtetrahydrofuran (THF). A molar reactant stoichiometry of 1CrCl₂ and2NaPy resulted in the isolation of a polymeric material, Product II, asthe major product and a pentanuclear complex, Product I, (Cr₅ (NC₄ H₄)₁₀(OC₄ H₈)₄), as the minor product, see Equation 1. Using molar excess ofNaPy resulted in the isolation of the dianionic square planar complex{Cr(NC₄ H₄)₄,}{Na}₂. 2OC₄ H₈, Product III, and the octahedral complex{Cr(C₄ H₄ N)₅ (OC₄ H₈)}{Na}₂. 4OC₄ H₈, Product IV, see Equation 2. Eachof the products was isolated through precipitation (Product II) orcrystallization (Products I, III, IV) from THF solutions by the additionof pentane. ##STR1##

EXAMPLE I

To prepare the pentanuclear complex, Product I, (Cr₅ (NC₄ H₄)₁₀ (OC₄H₈)₄), and the polymeric material, Product II, chromous chloride (2.0g/16.27 mmole) was combined with sodium pyrrolide (33.68 mmole) intetrahydrofuran and refluxed 20 hours. The reaction mixture was filtered(medium porosity frit) and the filtrate was used for fractionalcrystallization of both (Cr₅ (NC4H₄)₁₀ (OC₄ H₈)₄), Product I, and thepolymeric material, Product II, through the addition of pentane. Thepolymeric material crystallized as a blue solid followed by (Cr₅ (NC₄H₄)₁₀ (OC₄ H₈)₄) as opaque dark blue/purple crystals.

Analysis calculated for C₅₆ H₇₂ N₁₀ O₄ Cr₅, Product I: C, 55.62; H,6.00; N, 11.58%, by weight. Found: C, 55.46; H, 6.32; N, 11.15%, byweight. Analysis found for Product II: Cr, 11.5; C, 59.75; H, 7.61; N,9.17%, by weight, but variable upon precipitation conditions. An x-raycrystal structure of Product I showed a pentanuclear complexincorporating bridging amido-pyrrolyl, terminal amido-pyrrolyl, andtetrahydrofuran ligands (FIGS. 1 and 2).

EXAMPLE II

To prepare {Cr(NC₄ H₄)₄ }{Na}₂.2OC₄ H₈, Product III, and {Cr(C₄ H₄N)₅(OC₄ H₈)}{Na}₂.4OC₄ H₈, Product IV, chromous chloride (3.0 g/24.4mmole) was combined with sodium pyrrolide (100.9 mmole) intetrahydrofuran and refluxed 2 hours, see Equation 2. The reactionmixture was filtered (medium porosity frit) and the filtrate was usedfor fractional crystallization of both {Cr(NC₄ H₄)₄ }{Na}₂.2OC₄ H₈,Product III, and {Cr(C₄ H₄ N)₅ (OC₄ H₈)}{Na}₂.4OC₄ H₈, Product IV,through the addition of pentane. Product III crystallized as translucentorange/red crystals followed by Product IV as translucent purplecrystals. While not wishing to be bound by theory, the formation ofProduct IV is believed to result from the presence of chromic chloridein the chromous chloride reagent (Alfa, chromium (II) chloride,anhydrous, contains 5-10% by weight CrCl₃) used in the preparation.

Analysis calculated for C₂₄ H₃₂ N₄ O₂ CrNa₂, Product III: C, 56.94; H,6.32; N, 11.07% by weight. Found: C, 57.04; H, 6.30; N, 10.92%, byweight. Analysis calculated for C₄₀ H₆₀ N₅ O₅ CrNa₂, Product IV: C,60.90; H, 7.67; N, 8.88% by weight. Found: C, 60.81; H, 7.74; N, 9.44%,by weight. An x-ray crystal structure of Product III showed a squareplanar complex incorporating terminal amido-pyrrolyl ligands (FIG. 4).An x-ray crystal structure of Product IV showed an octahedral complexincorporating terminal amido-pyrrolyl and a tetrahydrofuran ligand(FIGS. 5 and 6).

EXAMPLE III

The reaction product obtained from sodium pyrrolide and CrCl₃ was themost preferred in the preparation of an active catalyst. Pyrrole (7.0ml/100.9 mmole) was mixed with NaH (4.2 g of 60%, about 105 mmole) indimethoxyethane at ambient temperature until bubbling ceased. Chromicchloride (5.33 g/33.7 mmole) was added to the solution at ambienttemperature. The reaction mixture was refluxed under nitrogen for fivehours, see Equation 3. This resulted in a dark green solution. Thesolution was filtered (medium porosity frit) and stripped of solventunder vacuum and pumped dry under vacuum for 12 hours. The resultantchromium pyrrolide complex was a green solid, Product V. It was used inthe preparation of an active catalyst without further purification.##STR2##

EXAMPLE IV

All single crystal x-ray structure analyses were performed byCrystalytics Company, Lincoln, Nebraska. Examples IV, V, VI, and IXcontain the resultant analytical and subsequently computer-generateddata.

A single crystal x-ray structure was obtained for Cr₅ (NC₄ H₄)₁₀ (OC₄H₈)₄ !, Product I, and shown in FIGS. 1 and 2. The description of thesingle-crystal sample and mounting used for data collection are asfollows:

Color: Dark blue

Shape: Rectangular parallelepiped

Dimensions: 0.20×0.48×0.80 mm

Crystal Mount: Crystal was sealed inside a thin-walled glass capillarywith epoxy under N₂.

Crystal Orientation: Crystal was oriented with its longest edge nearlyparallel to the phi axis of the diffractometer.

Width at half-height from ω Scans: 0.380°

The space group and cell data are as follows:

Crystal System: Triclinic

Space Group and Number: P1-C_(i) (No. 2)

Number of Computer-Centered Reflections Used in the Least-SquaresRefinement of the Cell Dimensions:

15 20>25° °C=20±1°

Lattice Constants with esd's:

    ______________________________________                                        a = 10.803(2)Å                                                                         α= 85.59(2)°                                                                  V = 1407.9(6)Å.sup.3                            b = 9.825(2)Å                                                                          β= 96.23(2)°                                                                   Z = 1                                               c = 14.212(4)Å                                                                         γ= 109.99(2)°                                                                 λ= 0.71073Å                              ______________________________________                                    

Molecular Weight: 1209.24 amu

Calculated Density: 1.427 g/cm⁻¹

Linear Absorption Coefficient: 0.96 mm⁻¹

Tables I-V list the resultant parameters used to generate the molecularstructures shown in FIGS. 1 and 2.

                  TABLE I                                                         ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in                                   Crystalline  Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4      ! .sup.a                                                                                                 Equivalent Isotropic                               Atom   Fractional Coordinates                                                                            Thermal Parameter,                                 Type .sup.b                                                                          10.sup.4 x                                                                             10.sup.4 y                                                                              10.sup.4 z                                                                           B, A.sup.2 × 10 .sup.c                 ______________________________________                                        Cr.sub.1                                                                             0 .sup.d 0 .sup.d  0/ .sup.d                                                                            25 (1)                                       Cr.sub.2                                                                             636(1)   2281(1)   1500(1)                                                                              24(1)                                        Cr.sub.3                                                                             -1179(1) 841(1)    3122(1)                                                                              28(1)                                        N.sub.1a                                                                             -1155(3) 935(3)    715(2) 25(1)                                        C.sub.1a                                                                             -2195(4) 64(4)     1231(3)                                                                              31(1)                                        C.sub.2a                                                                             -3313(4) 390(5)    965(3) 41(1)                                        C.sub.3a                                                                             -3014(4) 1486(5)   257(3) 43(1)                                        C.sub.4a                                                                             -1728(4) 1791(4)   116(3) 34(1)                                        N.sub.1b                                                                             1566(3)  1902(3)   331(2) 29(1)                                        C.sub.1b                                                                             1753(4)  3095(4)   -308(3)                                                                              36(1)                                        C.sub.2b                                                                             3035(5)  3751(5)   -432(3)                                                                              51(2)                                        C.sub.3b                                                                             3736(4)  2986(5)   131(3) 51(2)                                        C.sub.4b                                                                             2823(4)  1865(4)   587(3) 38(1)                                        N.sub.1c                                                                             -320(3)  2997(3)   2480(2)                                                                              27(1)                                        C.sub.1c                                                                             375(4)   3732(4)   3273(3)                                                                              34(1)                                        C.sub.2c                                                                             29(5)    4919(4)   3383(3)                                                                              43(1)                                        C.sub.3c                                                                             -908(5)  4967(4)   2631(3)                                                                              42(1)                                        C.sub.4c                                                                             -1105(4) 3809(4)   2101(3)                                                                              32(1)                                        N.sub.1d                                                                             443(3)   350(3)    2743(2)                                                                              28(1)                                        C.sub.1d                                                                             1600(4)  715(4)    3289(3)                                                                              36(1)                                        C.sub.2d                                                                             2321(4)  -133(5)   3102(3)                                                                              46(2)                                        C.sub.3d                                                                             1567(5)  -1070(5)  2403(3)                                                                              46(2)                                        C.sub.4d                                                                             422(4)   -763(4)   2203(3)                                                                              36(1)                                        N.sub.1e                                                                             -1972(3) -1122(3)  3801(2)                                                                              35(1)                                        C.sub.1e                                                                             -1344(5) -2107(4)  4069(3)                                                                              41(1)                                        C.sub.2e                                                                             -2189(5) -3307(4)  4503(3)                                                                              44(1)                                        C.sub.3e                                                                             -3361(5) -3061(4)  4531(3)                                                                              47(1)                                        C.sub.4e                                                                             -3206(5) -1731(4)  4097(3)                                                                              47(1)                                        O.sub.1f                                                                             2351(3)  3985(3)   1883(2)                                                                              32(1)                                        C.sub.1f                                                                             3536(4)  4018(4)   2483(3)                                                                              43(1)                                        C.sub.2f                                                                             4470(6)  5479(6)   2336(5)                                                                              76(2)                                        C.sub.3f                                                                             3642(5)  6408(5)   2147(4)                                                                              62(2)                                        C.sub.4f                                                                             2396(4)  5463(4)   1635(3)                                                                              40(1)                                        O.sub.1g                                                                             -2551(3) 1543(3)   3659(2)                                                                              35(1)                                        C.sub.1g                                                                             -3763(4) 1733(5)   3232(3)                                                                              44(1)                                        C.sub.2g                                                                             -4097(5) 2625(6)   3907(4)                                                                              57(2)                                        C.sub.3g                                                                             -3524(5) 2241(6)   4845(3)                                                                              57(2)                                        C.sub.4g                                                                             -2319(5) 1977(6)   4633(3)                                                                              50(2)                                        ______________________________________                                         .sup.a The numbers in Parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 1                             .sup.c This is onethird of the trace of the Orthogonalized Bjj tensor.        .sup.d This is a Symmetryrequired value and is therefore listed without a     estimated standard deviation.                                            

                  TABLE II                                                        ______________________________________                                        Anisotropic Thermal Parameters for Nonhydrogen                                Atoms in Crystalline  Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4            H.sub.8).sub.4 !.sup.a,b                                                      Atom  Anisotropic Thermal Parameter (Å.sup.2 × 10)                  Type.sup.c                                                                          B.sub.11                                                                             B.sub.22 B.sub.33                                                                           B.sub.12                                                                              B.sub.13                                                                            B.sub.23                             ______________________________________                                        Cr.sub.1                                                                            20(1)  23(1)    32(1)                                                                               5(1)    5(1) -4(1)                                Cr.sub.2                                                                            23(1)  22(1)    27(1)                                                                               7(1)    3(1) -2(1)                                Cr.sub.3                                                                            27(1)  26(1)    34(1)                                                                              11(1)    8(1)  1(1)                                N.sub.1a                                                                            21(1)  27(1)    29(1)                                                                               8(1)    1(1) -2(1)                                C.sub.1a                                                                            28(2)  31(2)    30(2)                                                                               4(1)    8(1) -4(1)                                C.sub.2a                                                                            23(2)  49(2)    49(2)                                                                               8(2)    5(2) -16(2)                               C.sub.3a                                                                            31(2)  51(2)    52(2)                                                                              22(2)   -7(2) -11(2)                               C.sub.4a                                                                            36(2)  32(2)    34(2)                                                                              15(1)   -2(1) -3(1)                                N.sub.1b                                                                            24(1)  25(1)    35(1)                                                                               3(1)    5(1) -4(1)                                C.sub.1b                                                                            40(2)  31(2)    33(2)                                                                               2(1)   11(1) -1(1)                                C.sub.2b                                                                            46(2)  42(2)    54(2)                                                                              -7(2)   24(2) -5(2)                                C.sub.3b                                                                            25(2)  50(2)    71(3)                                                                              -3(2)   15(2) -27(2)                               C.sub.4b                                                                            29(2)  38(2)    48(2)                                                                              10(1)    0(2) -15(2)                               N.sub.1c                                                                            28(1)  25(1)    30(1)                                                                              11(1)    3(1) -2(1)                                C.sub.1c                                                                            36(2)  35(2)    31(2)                                                                              10(1)    4(1) -3(1)                                C.sub.2c                                                                            52(2)  34(2)    43(2)                                                                              13(2)    6(2) -13(1)                               C.sub.3c                                                                            51(2)  31(2)    50(2)                                                                              22(2)    5(2) -5(2)                                C.sub.4c                                                                            35(2)  34(2)    31(2)                                                                              16(1)    4(1)  1(1)                                N.sub.1d                                                                            32(1)  23(1)    31(1)                                                                              12(1)    6(1)  3(1)                                C.sub.1d                                                                            33(2)  32(2)    42(2)                                                                               9(1)    6(2) -0(1)                                C.sub.2d                                                                            36(2)  50(2)    59(2)                                                                              24(2)    6(2) 11(2)                                C.sub.3d                                                                            61(3)  44(2)    47(2)                                                                              36(2)   11(2)  3(2)                                C.sub.4d                                                                            49(2)  35(2)    31(2)                                                                              23(2)    4(2)  1(1)                                N.sub.1e                                                                            36(2)  30(1)    42(2)                                                                              13(1)   14(1)  4(1)                                C.sub.1e                                                                            46(2)  36(2)    46(2)                                                                              20(2)   10(2)  6(2)                                C.sub.2e                                                                            64(3)  30(2)    37(2)                                                                              15(2)    7(2)  4(1)                                C.sub.3e                                                                            55(3)  31(2)    46(2)                                                                              -1(2)   18(2) -0(2)                                C.sub.4e                                                                            39(2)  38(2)    62(2)                                                                               9(2)   17(2)  4(2)                                O.sub.1f                                                                            29(1)  25(1)    40(1)                                                                               6(1)   -1(1) -2(1)                                C.sub.1f                                                                            34(2)  44(2)    45(2)                                                                               9(2)   -8(2) -6(2)                                C.sub.2f                                                                            45(3)  67(3)    95(4)                                                                              -3(2)   -15(3)                                                                              -6(3)                                C.sub.3f                                                                            59(3)  34(2)    78(3)                                                                              -2(2)   -6(3) -9(2)                                C.sub.4f                                                                            45(2)  23(1)    48(2)                                                                               7(1)    6(2) -1(1)                                O.sub.1g                                                                            34(1)  41(1)    37(1)                                                                              19(1)    7(1) -1(1)                                C.sub.1g                                                                            31(2)  56(2)    50(2)                                                                              20(2)    4(2) -5(2)                                C.sub.2g                                                                            47(3)  65(3)    72(3)                                                                              35(2)    2(2) -12(2)                               C.sub.3g                                                                            60(3)  75(3)    50(2)                                                                              36(2)   16(2) -8(2)                                C.sub.4g                                                                            45(2)  77(3)    35(2)                                                                              27(2)    8(2) -5(2)                                ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b The form of the anisotropic thermal parameter is given in referenc     8 on page 6 of the structure report.                                          .sup.c Atoms are labeled in agreement with FIG. 1.                       

                  TABLE III                                                       ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in                                      Crystalline (Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4      ! .sup.a                                                                      Atom     Fractional Coordinates                                               Type .sup.b                                                                            10.sup.4 x    10.sup.4 y                                                                            10.sup.4 z                                     ______________________________________                                        H.sub.1a -2129         -661    1707                                           H.sub.2a -4154         -55     1219                                           H.sub.3a -3608         1937    -69                                            H.sub.4a -1267         2508    -339                                           H.sub.1b 1053          3405    -617                                           H.sub.2b 3405          4593    -834                                           H.sub.3b 4676          3202    189                                            H.sub.4b 3031          1158    1020                                           H.sub.1c 1013          3445    3687                                           H.sub.2c 364           5592    3881                                           H.sub.3c -1331         5685    2512                                           H.sub.4c -1704         3580    1540                                           H.sub.1d 1881          1460    3743                                           H.sub.2d 3177          -88     3396                                           H.sub.3d 1807          -1790   2120                                           H.sub.4d -291          -1252   1752                                           H.sub.1e -446          -1976   3968                                           H.sub.2e -1997         -4161   4742                                           H.sub.3e -4139         -3699   4803                                           H.sub.4e -3878         -1286   4012                                           H.sub.1fa                                                                              3351          3836    3136                                           H.sub.1fb                                                                              3882          3308    2299                                           H.sub.2fa                                                                              5068          5771    2893                                           H.sub.2fb                                                                              4965          5524    1806                                           H.sub.3fa                                                                              3462          6711    2728                                           H.sub.3fb                                                                              4068          7245    1757                                           H.sub.4fa                                                                              2417          5653    964                                            H.sub.4fb                                                                              1641          5625    1839                                           H.sub.1ga                                                                              -3631         2231    2623                                           H.sub.1gb                                                                              -4455         813     3162                                           H.sub.2ga                                                                              -5037         2381    3901                                           H.sub.2gb                                                                              -3704         3640    3750                                           H.sub.3ga                                                                              -4129         1385    5124                                           H.sub.3gb                                                                              -3307         3025    5266                                           H.sub.4ga                                                                              -2173         1220    5050                                           H.sub.4gb                                                                              -1565         2846    4703                                           ______________________________________                                         .sup.a Hydrogen atoms were included in the structure factor calculations      as idealize/atoms (assuming sp.sup.2  or sp.sup.3 hybridization of the        carbon atoms and a C--N bond length of 0.96Å) "riding" on their           respective carbon atoms. The isotropic thermal parameter of each hydrogen     atom was fixed at 1.2 times the equivaient isotropic thermal parameter of     the carbon atoms to which it is covalently bonded                             .sup.b Hydrogen atoms are labeled with the same numerical and literal         subscripts as their carbon atoms with an additional literal subscript (a      or b) where necessary to distinguish between hydrogen atoms bonded to the     same carbon.                                                             

                  TABLE IV                                                        ______________________________________                                        Bond Lengths Involving Nonhydrogen Atoms in                                   Crystalline  Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4      !.sup.a                                                                       Type.sup.b  Length, Å                                                                            Type.sup.b Length, Å                               ______________________________________                                        Cr.sub.1 .sup. . . . Cr.sub.2                                                             3.066(1)   O.sub.1f --C.sub.1f                                                                      1.451(5)                                    Cr.sub.2 .sup. . . . Cr.sub.3                                                             3.12l(1)   O.sub.1f --C.sub.4f                                                                      1.453(5)                                                           O.sub.1g --C.sub.1g                                                                      1.448(6)                                    Cr.sub. --N.sub.1a                                                                        2.153(3)   O.sub.1g --C.sub.4g                                                                      1.451(5)                                    Cr.sub.1 --N.sub.1b                                                                       2.092(3)                                                          Cr.sub.2 --N.sub.1a                                                                       2.178(3)   C.sub.1a -C.sub.2a                                                                       1.360(6)                                    Cr.sub.2 --N.sub.1b                                                                       2.149(3)   C.sub.2a -C.sub.3a                                                                       1.395(6)                                    Cr.sub.2 --N.sub.1c                                                                       2.112(4)   C.sub.3a -C.sub.4a                                                                       1.351(6)                                    Cr.sub.3 --N.sub.1c                                                                       2.172(3)   C.sub.1b -C.sub.2b                                                                       1.338(6)                                    Cr.sub.3 --N.sub.1d                                                                       2.101(4)   C.sub.2b -C.sub.3b                                                                       1.393(7)                                    Cr.sub.3 --N.sub.1e                                                                       2.037(3)   C.sub.3b -C.sub.4b                                                                       1.376(6)                                                           C.sub.1c -C.sub.2c                                                                       1.365(7)                                    C.sub.r2 --O.sub.1f                                                                       2.082(2)   C.sub.2c -C.sub.3c                                                                       1.400(6)                                    C.sub.r3 --O.sub.1g                                                                       2.068(3)   C.sub.3c -C.sub.4c                                                                       1.356(6)                                                           C.sub.1d -C.sub.2d                                                                       1.376(7)                                    N.sub.1a --C.sub.1a                                                                       1.399(4)   C.sub.2d -C.sub.3d                                                                       1.396(6)                                    N.sub.1a --C.sub.4a                                                                       1.397(5)   C.sub.3d -C.sub.4d                                                                       1.367(8)                                    N.sub.1b --C.sub.1b                                                                       1.398(5)   C.sub.1e -C.sub.2e                                                                       1.370(5)                                    N.sub.1b --C.sub.4b                                                                       1.379(6)   C.sub.2e -C.sub.3e                                                                       1.374(8)                                    N.sub.1c --C.sub.1c                                                                       1.368(4)   C.sub.3e -C.sub.4e                                                                       1.366(6)                                    N.sub.1c --C.sub.4c                                                                       1.394(6)                                                          N.sub.1d --C.sub.1d                                                                       1.349(5)   C.sub.1f -C.sub.2f                                                                       1.460(6)                                    N.sub.1d --C.sub.4d                                                                       1.377(5)   C.sub.2f -C.sub.3f                                                                       1.474(9)                                    N.sub.1e --C.sub.1e                                                                       1.370(6)   C.sub.3f -C.sub.4f                                                                       1.496(6)                                    N.sub.1e --C.sub.4e                                                                       1.361(6)   C.sub.1g -C.sub.2g                                                                       1.496(8)                                                           C.sub.2g -C.sub.3g                                                                       1.485(7)                                                           C.sub.3g -C.sub.4g                                                                       1.476(9)                                    ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 1.                       

                  TABLE V                                                         ______________________________________                                        Bond Angles Involving Nonhydrogen Atoms in                                    Crystalline  Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4      !.sup.a                                                                       Type.sup.b  Angle, deg                                                                              Type.sup.b Angle, deg                                   ______________________________________                                        N.sub.1a Cr.sub.1 N.sub.1b                                                                84.8(1)   Cr.sub.1 N.sub.1a Cr.sub.2                                                               90.2(1)                                      N.sub.1a Cr.sub.1 N.sub.1a,.sup.c                                                         180.0(-).sup.d                                                                          Cr.sub.1 N.sub.1a C.sub.1a                                                               121.2(2)                                     N.sub.1b Cr.sub.1 N.sub.1a,.sup.c                                                         95.2(1)   Cr.sub.2 N.sub.1a C.sub.1a                                                               118.0(2)                                     N.sub.1b Cr.sub.1 N.sub.1b,.sup.c                                                         180.0(-).sup.d                                                                          Cr.sub.1 N.sub.1a C.sub.4a                                                               113.4(2)                                                           Cr.sub.2 N.sub.1a C.sub.4a                                                               110.6(2)                                     N.sub.1a Cr.sub.2 N.sub.1b                                                                82.9(1)   C.sub.1a N.sub.1a C.sub.4a                                                               103.5(3)                                     N.sub.1a Cr.sub.2 N.sub.1c                                                                96.5(1)   Cr.sub.1 N.sub.1b Cr.sub.2                                                               92.6(1)                                      N.sub.1b Cr.sub.2 N.sub.1C                                                                168.9(l)  Cr.sub.1 N.sub.1b C.sub.1b                                                               117.9(2)                                     N.sub.1a Cr.sub.2 O.sub.1f                                                                162.4(l)  Cr.sub.2 N.sub.1b C.sub.1b                                                               107.6(3)                                     N.sub.1b Cr.sub.2 O.sub.1f                                                                89.5(1)   Cr.sub.1 N.sub.1b c.sub.4b                                                               120.6(3)                                     N.sub.1c Cr.sub.2 O.sub.1f                                                                87.9(1)   Cr.sub.2 N.sub.1b C.sub.4b                                                               113.0(3)                                                           C.sub.1b N.sub.1b C.sub.4b                                                               104.4(3)                                     N.sub.1c Cr.sub.3 N.sub.1d                                                                88.1(1)   Cr.sub.2 N.sub.1c Cr.sub.3                                                               93.5(1)                                      N.sub.1c Cr.sub.3 N.sub.1e                                                                176.5(1)  Cr.sub.2 N.sub.1c C.sub.1c                                                               121.4(3)                                     N.sub.1d Cr.sub.3 N.sub.1e                                                                93.5(1)   Cr.sub.3 N.sub.1c C.sub.1c                                                               100.0(2)                                     N.sub.1c Cr.sub.3 O.sub.1f                                                                88.8(1)   Cr.sub.2 N.sub.1c C.sub.4c                                                               116.1(2)                                     N.sub.1d Cr.sub.3 O.sub.1g                                                                170.4(1)  Cr.sub.3 N.sub.1c C.sub.4c                                                               121.5(2)                                     N.sub.1e Cr.sub.3 O.sub.1g                                                                89.1(1)   C.sub.1c N.sub.1c C.sub.4c                                                               104.2(3)                                                           Cr.sub.3 N.sub.1d C.sub.1d                                                               121.3(3)                                     N.sub.1a C.sub.1a C.sub.2a                                                                110.6(3)  Cr.sub.3 N.sub.1d C.sub.4d                                                               127.8(3)                                     C.sub.1a C.sub.2a C.sub.3a                                                                107.5(4)  C.sub.1d N.sub.1d C.sub.4d                                                               106.4(4)                                     C.sub.2a C.sub.3a C.sub.4a                                                                106.9(4)  Cr.sub.3 N.sub.1e C.sub.1.sup.e                                                          126.3(3)                                     C.sub.3a C.sub.4a N.sub.1a                                                                111.5(3)  Cr.sub.3 N.sub.1e C.sub.4e                                                               128.3(3)                                     N.sub.1b C.sub.1b C.sub.2b                                                                111.2(4)  C.sub.1e N.sub.1e C.sub.4e                                                               105.3(3)                                     C.sub.1b C.sub.2b C.sub.3b                                                                107.4(4)                                                          C.sub.2b C.sub.3b C.sub.4b                                                                107.O(4)  Cr.sub.2 O.sub.1f C.sub.1f                                                               131.5(2)                                     C.sub.3b C.sub.4b N.sub.1b                                                                110.1(4)  Cr.sub.2 O.sub.1f C.sub.4f                                                               118.9(2)                                     N.sub.1c C.sub.1c C.sub.2c                                                                110.9(4)  C.sub.1f O.sub.1f C.sub.4f                                                               109.1(3)                                     C.sub.1c C.sub.2c C.sub.3C                                                                106.8(4)  Cr.sub.3 O.sub.1g C.sub.1g                                                               131.9(3)                                     C.sub.2c C.sub.3c C.sub.4c                                                                107.2(4)  Cr.sub.3 O.sub.1g C.sub.4g                                                               118.6(3)                                     C.sub.3c C.sub.4c N.sub.1c                                                                110.9(3)  C.sub.1g O.sub.1g C.sub.4g                                                               109.5(4)                                     N.sub.1d C.sub.1d C.sub.2d                                                                110.3(4)                                                          C.sub.1d C.sub.2d C.sub.3d                                                                106.7(4)  O.sub.1f C.sub.1f C.sub.2f                                                               105.0(4)                                     C.sub.2d C.sub.3d C.sub.4d                                                                106.6(5)  C.sub.1f C.sub.2f C.sub.3f                                                               104.9(4)                                     C.sub.3d C.sub.4d N.sub.1d                                                                109.9(3)  C.sub.2f C.sub.3f C.sub.4f                                                               104.4(4)                                     N.sub.1e C.sub.1e C.sub.2e                                                                110.0(4)  C.sub.3f C.sub.4 O.sub.1f                                                                105.4(4)                                     C.sub.1e C.sub.2e C.sub.3e                                                                107.2(4)  O.sub.1g C.sub.1g C.sub.2g                                                               104.8(4)                                     C.sub.2e C.sub.3e C.sub.4e                                                                106.7(4)  C.sub.1g C.sub.2g C.sub.3g                                                               104.2(5)                                     C.sub.3e C.sub.4e N.sub.1e                                                                110.8(5)  C.sub.2g C.sub.3g C.sub.4g                                                               104.2(4)                                                           C.sub.3g C.sub.4g O.sub.1g                                                               106.1(4)                                     ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 1                             .sup.c Atoms labeled with a prime() are related to nonprimed atoms by the     symmetry operation -x, -y, -z where the fractional coordinates (x,y,z) ar     given in Table I.                                                             .sup.d This is a symmetryrequired value and is therefore listed without a     estimated standard deviation.                                            

EXAMPLE V

A single crystal x-ray structure was obtained for Cr(NC₄ H₄)₄, a portionof Product III and shown in FIG. 3. A single crystal x-ray structure wasobtained for Na!₂ Cr(NC₄ H₄)₄ !. 2(OC₄ H₈), Product III and shown inFIG. 4. The description of the single-crystal sample and mounting usedfor the data collection are as follows:

Color: Red-Orange

Shape: Rectangular parallelepiped

Dimensions: 0.50×0.55×0.65 mm

Crystal Mount: Crystal was glued to the inside of a thin-walled

glass capillary and sealed under N₂.

Crystal Orientation: Crystal was oriented with its longest edge nearlyparallel to the phi axis of the diffractometer.

Width at Half-height from ω Scans: 0.86°

The space group and cell data are as follows:

Crystal System: Monoclinic

Space Group and Number: C2/c-C_(2h) (no. 15)

Number of Computer-Centered Reflections Used in the Least-SquaresRefinement of the Cell Dimensions:

Dimensions: 15 20>25° °C=20+1°

Lattice Constants with esd's:

    ______________________________________                                        a = 9.522(2)Å                                                                            α = 90.00°                                                                     V = 2697(1)Å.sup.3                           b = 15.118(2)Å                                                                           β = 98.99(1)°                                                                   Z = 4                                            c = 18.967(3)Å                                                                           γ = 90.00°                                                                     λ = 0.71073Å                          ______________________________________                                    

Molecular Weight: 506.52 amu

Calculated Density: 1.248 g/cm⁻³

Linear Absorption Coefficient: 0.47 mm⁻¹

Tables VI-X list the resultant parameters used to generate the molecularstructures shown in FIGS. 3 and 4.

                  TABLE VI                                                        ______________________________________                                        Atomic Coordinates for Nonhydrogen Atomns in Crystalline                      (Na).sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 } - 2(OC.sub.4 H.sub.8).sup.a                                     Equivalent Isotropic                               Atom   Fractional Coordinates                                                                            Thermal Parameter                                  Type.sup.b                                                                           10.sup.4 x                                                                              10.sup.4 y                                                                             10.sup.4 z                                                                           B, Å.sup.2 × 10.sup.c              ______________________________________                                        Anion                                                                         Cr     0.sup.d   2982(1)  2500.sup.d                                                                           58(1)                                        N.sub.1                                                                              1901(4)   2924(2)  3183(2)                                                                              56(1)                                        N.sub.2                                                                              8.sup.d   4343(3)  2500.sup.d                                                                           52(1)                                        N.sub.3                                                                              8.sup.d   1612(3)  2500.sup.d                                                                           70(2)                                        C.sub.11                                                                             3241(5)   2958(3)  3008(3)                                                                              65(2)                                        C.sub.12                                                                             4224(6)   2768(3)  3587(3)                                                                              73(2)                                        C.sub.13                                                                             3513(7)   2638(4)  4146(3)                                                                              82(2)                                        C.sub.14                                                                             2094(7)   2734(4)  3884(3)                                                                              76(2)                                        C.sub.21                                                                             907(5)    4884(3)  2926(3)                                                                              68(1)                                        C.sub.22                                                                             582(4)    5753(3)  2766(3)                                                                              69(2)                                        C.sub.31                                                                             390(5)    1081(3)  1996(4)                                                                              94(2)                                        C.sub.32                                                                             326(7)    213(3)   2189(5)                                                                              133(6)                                       Cation                                                                        Na     2301(2)   6879(1)  1783(1)                                                                              69(1)                                        Solvent of Crystallization                                                    O.sub.1                                                                              2065(4)   5108(2)  838(2) 83(1)                                        C.sub.41                                                                             2759(11)  5174(5)  239(4) 143(4)                                       C.sub.42                                                                             2884(11)  4319(5)  -79(4) 148(4)                                       C.sub.43                                                                             1893(10)  3786(5)  264(5) 142(4)                                       C.sub.44                                                                             1699(9)   4231(4)  902(4) 120(3)                                       ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIGS. 3 and 4.                     .sup.c This is onethird of the trace of the orthogenalized B.sub.ij           tensor.                                                                       .sup.d This is a symmetryrequired value and is therefore listed without a     estimated standard deviation.                                            

                  TABLE VII                                                       ______________________________________                                        Anisotropic Thermal Parameters for Nonhydrogen atoms in                       Crystalline {Na}.sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 }-2(OC.sub.4 H.sub.8).s    up.a,b                                                                        Atom Anisotropic Thermal Parameter (Å.sup.2 × 10)                   Type.sup.c                                                                         B.sub.11 B.sub.22                                                                              B.sub.33                                                                              B.sub.12                                                                            B.sub.13                                                                             B.sub.23                           ______________________________________                                        Anion                                                                         Cr   64(1)    34(1)    55(1)  0.sup.d                                                                             15(1)  0.sup.d                            N.sub.1                                                                            69(2)    44(2)    56(2)   6(1) 12(1)   6(1)                              N.sub.2                                                                            64(3)    39(2)    56(3)  0.sup.d                                                                             16(2)  0.sup.d                            N.sub.3                                                                            65(3)    38(2)   107(4)  0.sup.d                                                                             14(3)  0.sup.d                            C.sub.11                                                                           78(3)    50(2)    70(3)   -6(2)                                                                              18(2)   2(2)                              C.sub.12                                                                           70(3)    62(3)    84(3)   4(2)  7(2)   -8(2)                             C.sub.13                                                                           103(4)   79(3)    58(3)   22(3)                                                                              -8(3)   0(2)                              C.sub.14                                                                           86(3)    86(3)    58(3)   16(3)                                                                              16(2)   5(2)                              C.sub.21                                                                           66(2)    45(2)    70(3)   -2(2)                                                                              15(2)   -6(2)                             C.sub.22                                                                           68(3)    38(2)   105(4)   -7(2)                                                                              27(2)   -9(2)                             C.sub.31                                                                           65(3)    61(3)   152(5)   6(2)  9(3)  -36(3)                             C.sub.32                                                                           71(5)    46(2)    266(15)                                                                               6(3) -20(6) -44(4)                             Cation                                                                        Na    70(1)   57(1)     81(1)                                                                               -2(1) 15(1) -15(1)                              Solvent of Crystallization                                                    C.sub.1                                                                             108(2)  65(2)     82(2)                                                                              -10(2) 38(2) -16(2)                              C.sub.41                                                                            222(8)  112(5)   116(5)                                                                              -46(5) 92(6) -22(4)                              C.sub.42                                                                            192(8)  168(8)   107(5)                                                                               12(6) 70(5) -32(5)                              C.sub.43                                                                            147(6)  109(6)   177(8)                                                                              -27(5) 48(6) -69(6)                              C.sub.44                                                                            177(6)  77(4)    124(5)                                                                              -21(4) 76(5) -14(3)                              ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b The form of the anisotropic thermal parameter is given in referenc     8 on page 6 of the structure report.                                          .sup.c Atoms are labeled in agreement with FIGS. 1 and 2.                     .sup.d This is a symmetryrequired value and is therefore listed without a     estimated standard deviation.                                            

                  TABLE VIII                                                      ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in                                      Crystalline {Na}.sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 } - 2(OC.sub.4             H.sub.8).sup.a                                                                Atom         Fractional Coordinates                                           Type.sup.b   10.sup.4 x 10.sup.4 y                                                                              10.sup.4 z                                  ______________________________________                                        Anion                                                                         H.sub.11     3456       3881      2541                                        H.sub.12     5235       2748      3680                                        H.sub.13     3922       2488      4628                                        H.sub.14     1341       2679      4164                                        H.sub.21     1665       4687      3285                                        H.sub.22     1071       6262      2985                                        H.sub.31     706        1274      1565                                        H.sub.32     483        -301      1937                                        Solvent of Crystallization                                                    H.sub.41a    2250       5576      -100                                        H.sub.41b    3710       5388      385                                         H.sub.42a    3756       4891      -1                                          H.sub.42b    2464       4348      -583                                        H.sub.43a    995        3707      -39                                         H.sub.43b    2326       3220      377                                         H.sub.44a    2295       3973      1304                                        H.sub.44b    723        4191      969                                         ______________________________________                                         .sup.a Hydrogen atoms were included in the structure factor calculations      as idealized atoms (assuming sp.sup.2 - or sp.sup.3 -hybridization of the     carbon atoms and a C--H bond length of 0.96Å) "riding" on their           respective carbon atoms. The isotropic thermal parameter of each hydrogen     atom was fixed at 1.2 times the equivalent isotropic thermal parameter of     the carbon atom to which it is covalently bonded.                             .sup.b Hydrogen atoms are labeled with the same numerical subscripts as       the carbon atoms to which they are covalently bonded with an additional       literal subscript (a or b) where necessary to distinguish between             hydrogens bonded to the same carbon.                                     

                  TABLE IX                                                        ______________________________________                                        Anion Bond lengths and Bond Angles                                            Involving Nonhydrogen atoms in Crystalline                                    {Na}.sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 } - 2(OC.sub.4 H.sub.8).sup.a          ______________________________________                                        Type .sup.b                                                                              Length, Å                                                                            Type .sup.b                                                                              Length, Å                                ______________________________________                                        Cr--N.sub.1                                                                              2.057(3)   C.sub.11 -C.sub.12                                                                       1.355(7)                                     Cr--N.sub.2                                                                              2.056(4)   C.sub.12 -C.sub.13                                                                       1.361(9)                                     Cr--N.sub.3                                                                              2.072(5)   C.sub.13 -C.sub.14                                                                       1.374(9)                                                           C.sub.21 -C.sub.22                                                                       1.372(6)                                     N.sub.1 --C.sub.11                                                                       1.369(7)   C.sub.22 -C.sub.22,.sup.c                                                                1.379(9)                                     N.sub.1 --C.sub.14                                                                       1.344(6)   C.sub.31-C.sub.32                                                                        1.376(7)                                     N.sub.2 --C.sub.21                                                                       1.360(5)   C.sub.32 --C.sub.32,.sup.c                                                               1.327(18)                                    N.sub.3 --C.sub.31                                                                       1.344(7)                                                           ______________________________________                                        Type .sup.b                                                                              Angle, deg.                                                                              Type .sup.b                                                                              Angle, deg.                                  ______________________________________                                        N.sub.1 CrN.sub.2                                                                        92.5(1)    N.sub.1 C.sub.11 C.sub.12                                                                110.5(5)                                     N.sub.1 CrN.sub.3                                                                        87.5(1)    C.sub.11 C.sub.12 C.sub.13                                                               107.3(5)                                     N.sub.1 CrN.sub.1,.sup.c                                                                 175.1(2)   C.sub.12 C.sub.13 C.sub.14                                                               106.4(5)                                     N.sub.2 CrN.sub.3                                                                        180.0(-).sup.d                                                                           N.sub.1 C.sub.14 C.sub.13                                                                110.9(5)                                                           N.sub.2 C.sub.21 C.sub.22                                                                110.2(4)                                     CrN.sub.1 C.sub.11                                                                       127.5(5)   C.sub.21 C.sub.22 C.sub.22,.sup.c                                                        106.8(3)                                     CrN.sub.1 C.sub.14                                                                       127.1(4)   N.sub.3 C.sub.31 C.sub.32                                                                109.1(6)                                     C.sub.11 N.sub.1 C.sub.14                                                                104.9(4)   C.sub.31 C.sub.32 C.sub.32,.sup.c                                                        107.5(5)                                     CrN.sub.2 C.sub.21                                                                       127.0(2)                                                           C.sub.21 N.sub.2 C.sub.21,.sup.c                                                         106.0(5)                                                           CrN.sub.3 C.sub.31                                                                       126.7(3)                                                           C.sub.31 N.sub.3 C.sub.31,.sup.c                                                         106.7(6)                                                           ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 4.                            .sup.c Atoms labeled with a prime (') are related to nonprimed atoms by       the symmetry operation -x,y,1/2-z.                                       

                  TABLE X                                                         ______________________________________                                        Bond Lengths and Angles Involving the                                         Nonhydrogen Atoms of the Cation and                                           Solvent of Crystallization in                                                 {Na}.sub.2 (Cr(NC.sub.4 H.sub.4).sub.4) - 2(OC.sub.4 H.sub.8).sup.a           ______________________________________                                        Type .sup.b                                                                              Length, Å                                                                            Type .sup.b                                                                              Length, Å                                ______________________________________                                        Na--O.sub.1                                                                              2.313(4)   O.sub.1 --C.sub.41                                                                       1.390(10)                                                          O.sub.1 --C.sub.44                                                                       1.382(7)                                     Na . . . N.sub.1" .sup.c                                                                 2.888(4)                                                           Na . . . N.sub.3" .sup.c                                                                 2.830(4)   C.sub.41 -C.sub.42                                                                       1.43(1)                                                            C.sub.42 -C.sub.43                                                                       1.42(1)                                                            C.sub.43 -C.sub.44                                                                       1.42(1)                                      ______________________________________                                        Type .sup.b                                                                              Angle, deg.                                                                              Type .sup.b                                                                              Angle, deg.                                  ______________________________________                                        O.sub.1 NaN.sub.1".sup.c                                                                 128.6(3)   C.sub.41 O.sub.1 C.sub.44                                                                107.9(5)                                     O.sub.1 NaN.sub.3".sup.c                                                                 121.8(3)                                                           N.sub.1" NaN.sub.3".sup.c                                                                59.9(3)    O.sub.1 C.sub.41 C.sub.42                                                                109.O(7)                                                           C.sub.41 C.sub.42 C.sub.43                                                               105.0(8)                                     NaO.sub.1 C.sub.41                                                                       125.7(4)   C.sub.42 C.sub.43 C.sub.44                                                               107.0(7)                                     NaO.sub.1 C.sub.44                                                                       121.8(4)   O.sub.1 C.sub.44 C.sub.43                                                                107.6(7)                                     ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 4.                            .sup.c Atoms labeled with a double prime (") are related to nonprimed         atoms by the symmetry operation 1/3-x,1/3-y,1/3-z.                       

EXAMPLE VI

Single crystal x-ray structures were obtained for Cr(NC₄ H₄)₅ (OC₄ H₈)!,shown in FIG. 5, and Cr(NC₄ H₄)₅ (OC₄ H₈)! Na!₂.4(OC₄ H₈, Product IV,and shown in FIG. 6. The description of the single-crystal sample andmounting used for data collection are as follows:

Color: Purple

Shape: Rectangular parallelepiped

Dimensions: 0.50×0.55×0.63 mm

Crystal Mount: Crystal was glued to the inside of a thin-walled glasscapillary and sealed under N₂.

Crystal Orientation: Crystal was oriented with its longest edge nearlyparallel to the phi axis of the diffractometer.

Width at Half-height from ω Scans: 0.42°

The space group and cell data are as follows:

Crystal System: Monoclinic

Space Group and Number: P2₁ -C₂ (No. 4)

Number of Computer-Centered Reflections Used in the Least-Squares

Refinement of the Cell Dimensions:

15 20>20° °C=20±1°

Lattice Constants with esd's:

    ______________________________________                                        a = 10.042(2)Å                                                                          α = 90.00°                                                                     V = 2162(1)Å.sup.3                            b = 17.242(4)Å                                                                          β = 106.54(2)°                                                                  Z = 2                                             c = 13.025(3)Å                                                                          γ = 90.00°                                                                     λ = 0.71073Å                           ______________________________________                                    

Molecular Weight=788.93 amu

Calculated Density: 1.212 g/cm⁻³

Linear Absorption Coefficient: 0.32 mm⁻¹

Tables XI-XV list the resultant parameters used to generate themolecular structures shown in FIGS. 5 and 6.

                  TABLE XI                                                        ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in                                   Crystalline  Cr(NC.sub.4 N.sub.4).sub.5 (OC.sub.4 N.sub.8)! Na!.sub.2 -       4(OC.sub.4 N.sub.8).sup.a                                                                                 Equivalent                                                                    Isotropic Thermal                                 Atom   Fractional Coordinates                                                                             Parameter,                                        Type.sup.b                                                                           10.sup.4 x                                                                              10.sup.4 y                                                                             10.sup.4 z                                                                            B, Å.sup.2 × 10.sup.c             ______________________________________                                        Anion                                                                         Cr     198(1)    1477     2531(1) 32(1)                                       N.sub.1a                                                                             1694(5)   2026(3)  2028(4) 40(2)                                       C.sub.1a                                                                             1749(7)   2782(4)  1742(6) 48(2)                                       C.sub.2a                                                                             2929(8)   2926(5)  1420(7) 66(3)                                       C.sub.3a                                                                             3661(7)   2236(5)  1554(6) 62(3)                                       C.sub.4a                                                                             2899(6)   1695(5)  1913(5) 52(2)                                       N.sub.1b                                                                             1651(5)   1087(3)  3885(4) 40(2)                                       C.sub.1b                                                                             1463(8)   560(4)   4575(5) 48(2)                                       C.sub.2b                                                                             2572(9)   518(6)   5423(8) 82(4)                                       C.sub.3b                                                                             3554(8)   1064(6)  5275(6) 70(3)                                       C.sub.4b                                                                             2952(6)   1382(5)  4340(5) 48(2)                                       N.sub.1c                                                                             -1326(5)  1888(3)  1250(4) 38(2)                                       C.sub.1c                                                                             -1200(8)  2172(4)  266(6)  51(2)                                       C.sub.2c                                                                             -2458(8)  2270(5)  -476(6) 58(3)                                       C.sub.3c                                                                             -3435(8)  2038(6)  56(7)   75(3)                                       C.sub.4c                                                                             -2710(7)  1826(5)  1091(6) 56(3)                                       N.sub.1d                                                                             -32(5)    2455(4)  3445(5) 43(2)                                       C.sub.1d                                                                             504(7)    2562(5)  4505(6) 49(2)                                       C.sub.2d                                                                             107(9)    3278(5)  4774(8) 72(3)                                       C.sub.3d                                                                             -698(8)   3629(5)  3832(6) 59(3)                                       C.sub.4d                                                                             -769(7)   3108(4)  3055(6) 52(2)                                       N.sub.1e                                                                             315(5)    505(4)   1690(4) 40(2)                                       C.sub.1e                                                                             -574(8)   277(5)   704(6)  55(3)                                       C.sub.2e                                                                             -197(10)  -432(5)  403(7)  67(3)                                       C.sub.3e                                                                             990(10)   -662(6)  1256(8) 79(4)                                       C.sub.4e                                                                             1265(8)   -92(4)   2016(7) 51(3)                                       O.sub.1f                                                                             -1356(4)  926(3)   3083(4) 43(1)                                       C.sub.1f                                                                             -2047(7)  1244(5)  3800(6) 57(3)                                       C.sub.2f                                                                             -3263(10) 713(6)   3706(9) 98(5)                                       C.sub.3f                                                                             -2833(11) -21(6)   3402(8) 93(4)                                       C.sub.4f                                                                             -1903(8)  171(5)   2724(7) 64(3)                                       Cation 1                                                                      Na.sub.1                                                                             2254(3)   3336(2)  3737(3) 75(1)                                       Cation 2                                                                      Na.sub.2                                                                             1430(3)   974(2)   126(2)  62(1)                                       Solvent Molecules af Crystallization                                          O.sub.1g                                                                             4576(6)   3329(4)  4706(5) 83(2)                                       C.sub.1g                                                                             5748(9)   3100(10) 4433(9) 125(6)                                      C.sub.2g                                                                             6723(12)  2831(11) 5281(9) 145(7)                                      C.sub.3g                                                                             6503(15)  3272(11) 6146(11)                                                                              204(8)                                      C.sub.4g                                                                             5037(14)  3498(11) 5737(10)                                                                              170(8)                                      O.sub.1h                                                                             2342(7)   4602(4)  3279(6) 97(3)                                       C.sub.1h                                                                             1316(11)  5151(7)  2894(10)                                                                              112(5)                                      C.sub.2h                                                                             2017(16)  5830(9)  2541(11)                                                                              153(7)                                      C.sub.3h                                                                             3180(12)  5561(10) 2425(10)                                                                              131(6)                                      C.sub.4h                                                                             3551(13)  4848(7)  3070(11)                                                                              115(6)                                      O.sub.1i                                                                             1391(7)   1752(4)  -1377(4)                                                                              80(2)                                       C.sub.1i                                                                             2235(19)  1594(11) -1998(13)                                                                             160(8)                                      C.sub.2i                                                                             2716(17)  2287(14) -2337(15)                                                                             165(10)                                     C.sub.3i                                                                             1991(28)  2906(11) -1934(14)                                                                             204(12)                                     C.sub.4i                                                                             1010(16)  2533(7)  -1523(9)                                                                              128(6)                                      O.sub.1j                                                                             3037(5)   155(4)   -264(5) 72(2)                                       C.sub.1j                                                                             4389(10)  48(7)    427(9)  113(5)                                      C.sub.2j                                                                             4998(16)  -571(10) -23(16) 174(8)                                      C.sub.3j                                                                             4001(11)  -840(8)  -1006(10)                                                                             127(6)                                      C.sub.4j                                                                             2728(11)  -493(7)  -974(8) 92(4)                                       ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIGS. 5 and 6.                     .sup.c This is onethird of the trace of the orthogonalized B.sub.ij           tensor.                                                                  

                  TABLE XII                                                       ______________________________________                                        Anisotropic Thermal Parameters for Nonhydrogen                                Atoms in Crystalline  Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)! NA!.s    ub.2 -                                                                        4(OC.sub.4 H.sub.8).sup.a                                                     Atom Anisotropic Thermal Parameter (Å.sup.2 × 10)                   Type.sup.c                                                                         B.sub.11                                                                              B.sub.22 B.sub.33                                                                            B.sub.12                                                                             B.sub.13                                                                            B.sub.23                             ______________________________________                                        Anion                                                                         Cr   29(1)   31(1)    38(1)  1(1)  12(1)  1(1)                                N.sub.1a                                                                           33(2)   44(3)    44(3) -1(2)  11(2)  5(2)                                C.sub.1a                                                                           48(4)   37(3)    59(4) -0(3)  15(3)  3(3)                                C.sub.2a                                                                           55(4)   61(5)    90(5) -19(4) 34(4) 13(4)                                C.sub.3a                                                                           37(3)   82(6)    76(5) -9(3)  33(3)  2(4)                                C.sub.4a                                                                           40(3)   64(5)    52(4)  4(3)  16(3) -5(3)                                N.sub.1b                                                                           36(2)   44(3)    36(3)  7(2)   5(2) 12(2)                                C.sub.1b                                                                           52(4)   51(4)    40(3) -1(3)   9(3) 10(3)                                C.sub.2b                                                                           73(5)   85(6)    83(6)  2(5)  13(4) 44(5)                                C.sub.3b                                                                           51(4)   88(6)    54(4)  0(4)  -13(3)                                                                              12(4)                                C.sub.4b                                                                           41(3)   55(4)    45(3)  0(3)   5(2)  4(4)                                N.sub.1c                                                                           33(2)   41(3)    39(3)  4(2)   9(2)  1(2)                                C.sub.1c                                                                           52(4)   51(4)    51(4)  6(3)  16(3)  5(3)                                C.sub.2c                                                                           64(5)   62(5)    37(4) -1(4)  -4(3)  4(4)                                C.sub.3c                                                                           32(3)   92(6)    89(6)  4(4)  -3(4) 29(5)                                C.sub.4c                                                                           42(3)   78(5)    48(4) -1(3)   9(3) 14(4)                                N.sub.1d                                                                           31(2)   44(3)    56(3)  4(2)  13(2) -1(3)                                C.sub.1d                                                                           44(3)   60(5)    39(4) -5(3)   8(3) -11(3)                               C.sub.2d                                                                           63(4)   70(6)    84(6) -11(4) 20(4) -47(5)                               C.sub.3d                                                                           69(4)   43(4)    73(5)  9(3)  32(4) -14(4)                               C.sub.4d                                                                           42(3)   53(4)    63(4)  8(3)  17(3)  3(4)                                N.sub.1e                                                                           47(3)   36(3)    39(3) -3(2)  17(2) -7(2)                                C.sub.1e                                                                           59(4)   49(4)    53(4) -15(3) 11(3) -1(4)                                C.sub.2e                                                                           92(5)   48(4)    69(5) -20(4) 36(4) -26(4)                               C.sub.3e                                                                           91(6)   45(5)    106(7)                                                                               4(4)  37(5) -13(5)                               C.sub.4e                                                                           62(4)   23(3)    69(5)  7(3)  20(4) -7(3)                                O.sub.1f                                                                           40(2)   42(2)    51(2) -4(2)  20(2)  2(2)                                C.sub.1f                                                                           61(4)   64(5)    60(4) -2(3)  39(3)  4(4)                                C.sub.2f                                                                           81(6)   95(7)    144(8)                                                                              -24(5) 74(6)  1(6)                                C.sub.3f                                                                           109(7)  80(6)    177(7)                                                                              -26(5) 75(6) -3(6)                                C.sub.4f                                                                           61(4)   53(4)    85(5) -27(4) 30(4) -16(4)                               Cation 1                                                                      Na.sub.1                                                                           57(2)   71(2)    95(2) -13(1) 21(2) -2(2)                                Cation 2                                                                      Na.sub.2                                                                           68(2)   69(2)    56(2) -2(1)  30(1) -3(2)                                Solvent Molecules of Crystallization                                          O.sub.1g                                                                           58(3)   95(4)    92(4) -8(3)  15(3) -2(4)                                C.sub.1g                                                                           54(5)   215(14)  108(8)                                                                               0(7)  29(5) -7(9)                                C.sub.2g                                                                           96(7)   226(15)  121(9)                                                                              52(9)  43(7)  51(10)                              C.sub.3g                                                                           129(10) 277(19)  148(11)                                                                              52(12)                                                                              -56(9)                                                                              -134(13)                             C.sub.4g                                                                           134(10) 250(18)  128(10)                                                                              44(11)                                                                              39(9) -89(11)                              O.sub.1h                                                                           71(4)   68(4)    152(6)                                                                              -8(3)  32(4) -3(4)                                C.sub.1h                                                                           92(7)   95(8)    144(9)                                                                              -2(6)  28(7) -3(7)                                C.sub.2h                                                                           212(14) 108(9)   140(10)                                                                              36(10)                                                                               50(10)                                                                             66(9)                                C.sub.3h                                                                           99(8)   175(14)  101(8)                                                                              -6(9)  -2(6) 32(9)                                C.sub.4h                                                                           99(8)   79(7)    168(11)                                                                             -13(6) 38(8) 29(8)                                O.sub.1i                                                                           98(4)   82(4)    73(3)  8(3)  47(3) 13(3)                                C.sub.1i                                                                           230(15) 128(11)  168(12)                                                                              8(11) 131(12)                                                                              74(10)                              C.sub.2i                                                                           112(10) 222(21)  156(15)                                                                              1(12)  28(10)                                                                              23(16)                              C.sub.3i                                                                           370(26) 124(12)  135(12)                                                                             -93(15)                                                                               99(15)                                                                              34(10)                              C.sub.4i                                                                           223(13) 81(7)    106(8)                                                                              32(8)  91(9) 31(6)                                O.sub.1j                                                                           59(3)   64(3)    94(4)  5(3)  22(3) -21(3)                               C.sub.1j                                                                           88(7)   101(8)   133(9)                                                                              19(6)   2(6) -58(7)                               C.sub.2j                                                                           94(8)   190(14)  205(13)                                                                              73(10)                                                                              -11(9)                                                                              -90(13)                              C.sub.3j                                                                           83(7)   130(10)  160(10)                                                                             16(7)   20(7)                                                                              -86(9)                               C.sub.4j                                                                           82(6)   104(8)   92(7) -7(6)   29(5)                                                                              -41(6)                               ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b The form of the anisotropic thermal parameter is given in referenc     8 on page 6 of the structure report.                                          .sup.c Atoms are labeled in agreement with FIGS. 5 and 6.                

                  TABLE XIII                                                      ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in                                      Crystalline  Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)! Na!.sub. -        4(OC.sub.4 H.sub.8).sup.a                                                     Atom        Fractional Coordinates                                            Type.sup.b  10.sup.4 x 10.sup.4 y 10.sup.4 z                                  ______________________________________                                        Anion                                                                         H.sub.1a    1061       3165       1756                                        H.sub.2a    3182       3406       1151                                        H.sub.3a    4547       2153       1428                                        H.sub.4a    3162       1162       2059                                        H.sub.1b    637        254        4479                                        H.sub.2b    2692       174        6022                                        H.sub.3b    4453       1179       5753                                        H.sub.4b    3373       1775       4016                                        H.sub.1c    -326       2281       132                                         H.sub.2c    -2637      2453       -1199                                       H.sub.3c    -4426      2031       -243                                        H.sub.4c    -3137      1655       1623                                        H.sub.1d    1070       2197       4997                                        H.sub.2d    349        3499       5480                                        H.sub.3d    -1115      4135       3762                                        H.sub.4d    -1278      3184       2317                                        H.sub.1e    -1346      578        293                                         H.sub.2e    -630       -712       -243                                        H.sub.3e    1503       -1135      1285                                        H.sub.4e    1999       -107       2676                                        H.sub.1fa   -1447      1250       4520                                        H.sub.1fb   -2359      1762       3588                                        H.sub.2fa   -4069      899        3170                                        H.sub.2b    -3468      674        4380                                        H.sub.3fa   -2341      -312       4022                                        H.sub.3fb   -3620      -314       2996                                        H.sub.4fa   -2417      184        1980                                        H.sub.4fb   -1165      -201       2831                                        Solvent of Crystallization                                                    H.sub.1ga   6103       3536       4135                                        H.sub.1gb   5503       2694       3909                                        H.sub.2ga   6629       2283       5371                                        H.sub.2gb   7629       2940       5209                                        H.sub.3ga   6644       2947       6766                                        H.sub.3gb   7102       3717       6322                                        H.sub.4ga   4960       4045       5839                                        H.sub.4gb   4493       3223       6118                                        H.sub.1ha   596        4950       2301                                        H.sub.1hb   921        5310       3451                                        H.sub.2ha   2205       6231       3073                                        H.sub.2hb   1449       6034       1874                                        H.sub.3ha   3066       5447       1684                                        H.sub.3hb   3908       5936       2669                                        H.sub.4ha   4260       4953       3725                                        H.sub.4hb   3874       4459       2671                                        H.sub.1ia   3007       1289       -1594                                       H.sub.1ib   1721       1306       -2615                                       H.sub.2ia   3703       2328       -2031                                       H.sub.2ib   2496       2303       -3103                                       H.sub.3ia   1541       3249       -2509                                       H.sub.3ib   2638       3195       -1381                                       H.sub.4ia   101        2580       -2020                                       H.sub.4ib   1010       2761       -851                                        H.sub.1ja   4929       513        470                                         H.sub.1jb   4341       -91        1129                                        H.sub.2ja   5823       -388       -178                                        H.sub.2jb   5232       -992       479                                         H.sub.3ja   3930       -1396      -1018                                       H.sub.3jb   4261       -668       -1623                                       H.sub.4ja   2185       -862       -715                                        H.sub.4jb   2215       -324       -1678                                       ______________________________________                                         .sup.a Hydrogen atoms were included in the structure factor calculations      as idealized atoms (assuming sp.sup.2 or sp.sup.3 hybridization of the        carbon atoms and a C--H bond length of 0.96Å ) "riding" on their          respective carbon atoms. The isotropic thermal parameter of each hydrogen     atom was fixed at 1.2 times the equivalent isotropic thermal parameter of     the carbon atom to which it is covalently bonded.                             .sup.b Hydrogen atoms are labeled with the same numerical and literal         subscripts as their carbon atoms with an additionai literal subscript (a,     or b ) where necessary to distinguish between hydrogen atoms bonded to th     same carbon.                                                             

                  TABLE XIV                                                       ______________________________________                                        Bond Lengths Involving Nonhydrogen Atoms in                                   Crystalline  Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)! Na!.sub.2         -4(OC.sub.4 H.sub.8).sup.a                                                    Type.sup.b Length, Å                                                                             Type.sup.b                                                                              Length, Å                                ______________________________________                                        Cr-N.sub.1a                                                                              2.035(6)    Na.sub.1 -O.sub.1g                                                                      2.314(6)                                     Cr-N.sub.1b                                                                              2.056(5)    Na.sub.1 -O.sub.1h                                                                      2.271(8)                                     Cr-N.sub.1c                                                                              2.044(5)                                                           Cr-N.sub.1d                                                                              2.114(6)    Na.sub.2 -O.sub.1i                                                                      2.365(7)                                     Cr-N.sub.1e                                                                              2.024(6)    Na.sub.2 -O.sub.1j                                                                      2.307(7)                                     Cr-O.sub.1f                                                                              2.120(5)    C.sub.1g -C.sub.2g                                                                      1.33(2)                                                             C.sub.2g -C.sub.3g                                                                      1.43(2)                                      N.sub.1a -C.sub.1a                                                                       1.36(1)     C.sub.3g -C.sub.4g                                                                      1.47(2)                                      N.sub.1a -C.sub.4a                                                                       1.38(1)     C.sub.1h -C.sub.2h                                                                      1.51(2)                                      N.sub.1b -C.sub.1b                                                                       1.33(1)     C.sub.2h -C.sub.3h                                                                      1.30(2)                                      N.sub.1b -C.sub.4b                                                                       1.37(1)     C.sub.3h -C.sub.4h                                                                      1.48(2)                                      N.sub.1c -C.sub.1c                                                                       1.41(1)     C.sub.1i -C.sub.2i                                                                      1.41(3)                                      N.sub.1c -C.sub.4c                                                                       1.35(1)     C.sub.2i -C.sub.3i                                                                      1.47(3)                                      N.sub.1d -C.sub.1d                                                                       1.34(1)     C.sub.3i -C.sub.4i                                                                      1.40(3)                                      N.sub.1d -C.sub.4d                                                                       1.36(1)     C.sub.1j -C.sub.2j                                                                      1.44(2)                                      N.sub.1e -C.sub.1e                                                                       1.40(1)     C.sub.2j -C.sub.3j                                                                      1.46(2)                                      N.sub.1e -C.sub.4e                                                                       1.39(1)     C.sub.3j -C.sub.4j                                                                      1.42(2)                                      O.sub.1f -C.sub.1f                                                                       1.42(1)     O.sub.1g -C.sub.1g                                                                      1.38(1)                                      O.sub.1f -C.sub.4f                                                                       1.44(1)     O.sub.1g -C.sub.4g                                                                      1.32(1)                                                             O.sub.1h -C.sub.1h                                                                      1.38(1)                                      C.sub.1a -C.sub.2a                                                                       1.39(1)     O.sub.1h -C.sub.4h                                                                      1.39(2)                                      C.sub.2a -C.sub.3a                                                                       1.38(1)     O.sub.1i -C.sub.1i                                                                      1.36(2)                                      C.sub.3a -C.sub.4a                                                                       1.37(1)     O.sub.1i -C.sub.4i                                                                      1.40(1)                                      C.sub.1b -C.sub.2b                                                                       1.33(1)     O.sub.1j -C.sub.1j                                                                      1.41(1)                                      C.sub.2b -C.sub.3b                                                                       1.42(1)     O.sub.1j -C.sub.4j                                                                      1.43(1)                                      C.sub.3b -C.sub.4b                                                                       1.31(1)                                                            C.sub.1c -C.sub.2c                                                                       1.37(1)     Na.sub.1 -C.sub.1a                                                                      2.678(8)                                     C.sub.2c -C.sub.3c                                                                       1.41(1)     Na.sub.1 -N.sub.1d                                                                      2.688(7)                                     C.sub.3c -C.sub.4c                                                                       1.39(1)     Na.sub.1 -C.sub.1d                                                                      2.621(9)                                     C.sub.1d -C.sub.2d                                                                       1.37(1)                                                            C.sub.2d -C.sub.3d                                                                       1.40(1)                                                            C.sub.3d -C.sub.4d                                                                       1.34(1)     Na.sub.2 -C.sub.4a                                                                      2.681(7)                                     C.sub.1e -C.sub.2e                                                                       1.37(1)     Na.sub.2 -C.sub.1e                                                                      2.630(9)                                     C.sub.2e -C.sub.3e                                                                       1.43(1)                                                            C.sub.3e -C.sub.4e                                                                       1.37(1)                                                            C.sub.1f -C.sub.2f                                                                       1.50(1)                                                            C.sub.2f -C.sub.3f                                                                       1.43(2)                                                            C.sub.3f -C.sub.4f                                                                       1.49(2)                                                            ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 6.                       

                  TABLE XV                                                        ______________________________________                                        Bond Angles Invoicing Nonhydrogen Atoms in                                    Crystalline  Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)! Na!.sub.2         -4(OC.sub.4 H.sub.8).sup.a                                                    Type.sup.b                                                                             Angle, deg   Type.sup.b                                                                              Angle, deg                                    ______________________________________                                        N.sub.1a CrN.sub.1b                                                                    91.2(2)      O.sub.1g Na.sub.1 O.sub.1h                                                              92.3(3)                                       N.sub.1a CrN.sub.1c                                                                    91.4(2)      O.sub.1g Na.sub.1 C.sub.1a                                                              114.3(3)                                      N.sub.1a CrN.sub.1d                                                                    91.1(2)      O.sub.1g Na.sub.1 N.sub.1d                                                              139.6(3)                                      N.sub.1a CrN.sub.1e                                                                    92.8(2)      O.sub.1g Na.sub.1 C.sub.1d                                                              118.0(3)                                      N.sub.1a CrO.sub.1f                                                                    178.7(2)     O.sub.1h Na.sub.1 C.sub.1a                                                              95.6(3)                                       N.sub.1b CrN.sub.1c                                                                    176.2(2)     O.sub.1h Na.sub.1 N.sub.1d                                                              127.0(2)                                      N.sub.1b CrN.sub.1d                                                                    86.7(2)      O.sub.1h Na.sub.1 C.sub.1d                                                              132.1(3)                                      N.sub.1b CrN.sub.1e                                                                    93.3(2)      C.sub.1a Na.sub.1 N.sub.1d                                                              75.1(2)                                       N.sub.1b CrO.sub.1f                                                                    88.5(2)      C.sub.1a Na.sub.1 C.sub.1d                                                              103.1(3)                                      N.sub.1c CrN.sub.1d                                                                    90.4(2)      N.sub.1d Na.sub.1 C.sub.1d                                                              29.3(2)                                       N.sub.1c CrN.sub.1e                                                                    89.4(2)                                                              N.sub.1c CrO.sub.1f                                                                    88.8(2)      O.sub.1i Na.sub.2 O.sub.1j                                                              90.7(3)                                       N.sub.1d CrN.sub.1e                                                                    176.1(2)     O.sub.1i Na.sub.2 C.sub.4a                                                              109.3(3)                                      N.sub.1d CrO.sub.1f                                                                    87.6(2)      O.sub.1i Na.sub.2 C.sub.1e                                                              131.5(2)                                      N.sub.1e CrO.sub.1f                                                                    88.5(2)      O.sub.1j Na.sub.2 C.sub.4a                                                              103.2(2)                                                            O.sub.1j Na.sub.2 C.sub.1e                                                              115.1(3)                                      CrN.sub.1a C.sub.1a                                                                    128.7(5)     C.sub.4a Na.sub.2 C.sub.1e                                                              103.9(3)                                      CrN.sub.1a C.sub.4a                                                                    126.3(5)                                                             CrN.sub.1b C.sub.1b                                                                    127.0(4)     Na.sub.1 O.sub.1g C.sub.1g                                                              131.4(6)                                      CrN.sub.1b C.sub.4b                                                                    127.3(5)     Na.sub.1 O.sub.1g C.sub.4g                                                              124.0(8)                                      CrN.sub.1c C.sub.1c                                                                    128.5(5)     Na.sub.1 O.sub.1h C.sub.1h                                                              132.2(7)                                      CrN.sub.1c C.sub.4c                                                                    126.7(5)     Na.sub.1 O.sub.1h C.sub.4h                                                              116.6(6)                                      CrN.sub.1d C.sub.1d                                                                    127.7(5)     Na.sub.2 O.sub.1i C.sub.1i                                                              120.9(8)                                      CrN.sub.1d C.sub.4d                                                                    125.7(5)     Na.sub.2 O.sub.1i C.sub.4i                                                              126.8(7)                                      CrN.sub.1e C.sub.1e                                                                    127.7(5)     Na.sub.2 O.sub.1j C.sub.1j                                                              123.1(6)                                      CrN.sub.1e C.sub.4e                                                                    126.2(4)     Na.sub.2 O.sub.1j C.sub.4j                                                              125.8(5)                                      CrO.sub.1f C.sub.1f                                                                    126.4(4)     C.sub.1g O.sub.1g C.sub.4g                                                              104.3(8)                                      CrO.sub.1f C.sub.4f                                                                    123.1(5)     C.sub.1h O.sub.1h C.sub.4h                                                              108.9(9)                                                            C.sub.1i O.sub.1i C.sub.4i                                                              107.8(11)                                     C.sub.1a N.sub.1a C.sub.4a                                                             105.0(6)     C.sub.1j O.sub.1j C.sub.4j                                                              107.7(7)                                      C.sub.1b N.sub.1b C.sub.4b                                                             105.2(5)                                                             C.sub.1c N.sub.1c C.sub.4c                                                             104.0(5)     O.sub.1g C.sub.1g C.sub.2g                                                              111(1)                                        C.sub.1d N.sub.1d C.sub.4d                                                             106.6(6)     C.sub.1g C.sub.2g C.sub.3g                                                              103(1)                                        C.sub.1e N.sub.1e C.sub.4e                                                             106.0(6)     C.sub.2g C.sub.3g C.sub.4g                                                              103(1)                                                              C.sub.3g C.sub.4g O.sub.1g                                                              110(1)                                        C.sub.1f O.sub.1f C.sub.4f                                                             110.5(6)     O.sub.1h C.sub.1h C.sub.2h                                                              106(1)                                                              C.sub.1h C.sub.2h C.sub.3h                                                              106(1)                                        N.sub.1a C.sub.1a C.sub.2a                                                             111.1(7)     C.sub.2h C.sub.3h C.sub.4h                                                              109(1)                                        C.sub.1a C.sub.2a C.sub.3a                                                             106.1(8)     C.sub.3h C.sub.4h O.sub.1h                                                              106(1)                                        C.sub.2a C.sub.3a C.sub.4a                                                             107.5(7)     O.sub.1i C.sub.1i C.sub.2i                                                              110(2)                                        C.sub.3a C.sub.4a N.sub.1a                                                             110.3(7)     C.sub.1i C.sub.2i C.sub.3i                                                              105(2)                                        N.sub.1b C.sub.1b C.sub.2b                                                             110.6(7)     C.sub.2i C.sub.3i C.sub.4i                                                              106(2)                                        C.sub.1b C.sub.2b C.sub.3b                                                             107.6(8)     C.sub.3i C.sub.4i O.sub.1i                                                              107(1)                                        C.sub.2b C.sub.3b C.sub.4b                                                             104.4(7)     O.sub.1j C.sub.1j C.sub.2j                                                              106(1)                                        C.sub.3b C.sub.4b N.sub.1b                                                             112.2(7)     C.sub.1j C.sub.2j C.sub.3j                                                              109(1)                                        N.sub.1c C.sub.1c C.sub.2c                                                             112.4(7)     C.sub.2j C.sub.3j C.sub.4j                                                              104(1)                                        C.sub.1c C.sub.2c C.sub.3c                                                             104.5(7)     C.sub.3j C.sub.4j O.sub.1j                                                              108(1)                                        C.sub.2c C.sub.3c C.sub.4c                                                             107.8(7)                                                             C.sub.3c C.sub.4c N.sub.1c                                                             111.2(7)     Na.sub.1 C.sub.1a N.sub.1a                                                              95.0(4)                                       N.sub.1d C.sub.1d C.sub.2d                                                             109.0(7)     Na.sub.1 C.sub.1a C.sub.2a                                                              106.7(5)                                      C.sub.1d C.sub.2d C.sub.3d                                                             107.6(8)     Na.sub.1 N.sub.1d Cr                                                                    107.7(3)                                      C.sub.2d C.sub.3d C.sub.4d                                                             105.4(8)     Na.sub.1 N.sub.1d C.sub.1d                                                              72.6(4)                                       C.sub.3d C.sub.4d N.sub.1d                                                             111.5(7)     Na.sub.1 N.sub.1d C.sub.4d                                                              86.4(4)                                       N.sub.1e C.sub.1e C.sub.2e                                                             111.0(7)     Na.sub.1 C.sub.1d N.sub.1d                                                              78.1(4)                                       C.sub.1e C.sub.2e C.sub.3e                                                             105.2(7)     Na.sub.1 C.sub.1d C.sub.2d                                                              85.1(6)                                       C.sub.2e C.sub.3e C.sub.4e                                                             108.4(8)                                                             C.sub.3e C.sub.4e N.sub.1e                                                             109.5(7)     Na.sub.2 C.sub.4a N.sub.1a                                                              90.2(3)                                                             Na.sub.2 C.sub.4a C.sub.3a                                                              104.0(5)                                      O.sub.1f C.sub.1f C.sub.2f                                                             104.4(7)     Na.sub.2 C.sub.1e N.sub.1e                                                              78.1(4)                                       C.sub.1f C.sub.2f C.sub.3f                                                             105.0(9)     Na.sub.2 C.sub.1e C.sub.2e                                                              91.7(6)                                       C.sub.2f C.sub.3f C.sub.4f                                                             104.9(9)                                                             C.sub.3f C.sub.4f O.sub.1f                                                             104.7(7)                                                             ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 6.                       

EXAMPLE VII

The product obtained from the reaction of sodium 2,5-dimethylpyrrolideand CrCl₂ used in the preparation of an active catalyst was a light bluesolid, Product VI. 2,5-Dimethylpyrrole (5.0 ml/49.1 mmole) was mixedwith excess sodium (40% dispersion in mineral spirits) intetrahydrofuran (125 ml) at ambient temperature. The mixture wasrefluxed 12 hours under nitrogen then filtered to remove excess sodium.The sodium 2,5-dimethylpyrrolide was used in-situ and combined withchromous chloride (3.03 g/24.7 mmole) at ambient temperature. Thereaction mixture was refluxed under nitrogen for 48 hours. Thegray-green solution was filtered (medium porosity frit) at ambienttemperature and stripped of solvent under vacuum, then pumped dry undervacuum for 12 hours resulting in a gray/green solid. This gray/greensolid was then washed with pentane resulting in a light blue solid,Product VI, which was collected by filtration. Product VI was used inthe preparation of an active catalyst without further purification.

EXAMPLE VIII Preparation of Catalysts

All polymerization runs were carried out in a two liter reactor underslurry (particle form) conditions. The diluent was isobutane and thereactor temperature was 90° C. Reactor pressure held at 550 psig duringthe polymerization, with ethylene being fed on demand.

The actual charging of the reactor was accomplished by the followingmethod. After purging the reactor at 100° C. with a stream of nitrogenfor at least 15 minutes, the reactor temperature was lowered to 90° C.and a preweighed amount of supported chromium pyrrolide catalyst wascharged against a slight countercurrent of nitrogen. One liter ofisobutane was then charged to the reactor and finally the reactorpressurized with ethylene.

The ethylene consumed was determined using a precalibrated ethylene flowmeter. Samples of the liquid product mixture were taken after 30 minuterun time without depressurizing the reactor. This was done by filling to200-300 psig a steel sampling cylinder adapted to the reactor with a diptube fitted with a fritted tip extending into the bottom of the reactorvessel. Samples taken this way were analyzed by gas chromatography andgas chromatography-mass spectrometry. Selectivities were normalized to100%. Solid products were obtained by venting the reactor to atmosphere,separating by decantation of the liquids from the solid material. Thesolids were then dried at 100° C. in a vacuum oven and weighed. Theyield of solid product was obtained by weighing the combined solid andcatalyst residues and subtracting from this the preweighed catalystcharge. The yield of volatile products was obtained by subtracting theyield of solid products from the grams of ethylene consumed as recordedby the flow meter.

Activity typically ranged from 300-1500 g product/g catalyst/hourcalculated for 30 minute run time, as shown in Table XVI. The productobtained typically was represented by 97-99.5% by weight liquids and0.5-3% by weight polymer (wax). The liquid fraction was typically 85%hexenes, 11% decenes, 2% tetradecences, based on the total weight of theliquid fraction. The balance of the liquid product mixture was a tracelevel distribution of olefins typically totaling about 1-2% by weight ofthe product mixture, see Table XVII.

Active catalysts were prepared from the chromium pyrrolide complexes asfollows. All toluene and/or pentane rinses used about 15 to about 30 mlsof liquid.

Run 1: 0.158 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF, wasslurried with 15 ml toluene at ambient temperature. 9.0 ml of a 1M TEAin hexanes solution was added to the solution and stirred for 24 hours.The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. AlPO₄ (P/Al moleratio=0.4) (2.00 g) was added to the solution and stirred for anadditional 24 hours. The supported catalyst was filtered from thesolution as a brown solid, rinsed twice with toluene, and then twicewith pentane. 0.3143 g of the catalyst was charged directly to thereactor for polymerization. 1.0 ml of a 0.5% TEA in heptanes solutionwas charged to the reactor after the catalyst charge but before theisobutane (reactor solvent) charge to purge feedstock poisons.

Run 2: 0.081 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF, wasslurried with 15 ml diethylbenzene at ambient temperature. 2.0 ml of a1M TEA in hexanes solution was added to the solution and stirred for 24hours. The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. AlPO₄ (P/Al moleratio=0.4) (1.50 g) was added to the solution and stirred for anadditional 1 hour. The supported catalyst was filtered from the solutionas a brown solid, rinsed twice with dimethylbenzene, and then twice withpentane. 0.4333 g of the catalyst was charged directly to the reactorfor polymerization. 3.0 ml of a 0.5% TEA in heptanes solution wascharged to the reactor after the catalyst charge but before theisobutane (reactor solvent) charge to purge feedstock poisons.

Run 3: 0.093 g of Product V (prepared in DME solvent) was slurried with15 ml toluene at ambient temperature. 5.0 ml of a 1M TEA in hexanessolution was added to the solution and stirred for 24 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.0g) was added to the solution and stirred for an additional 24 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice with pentane. 0.1564 g of thecatalyst was charged directly to the reactor for polymerization. 3.0 mlof a 0.5% TEA in heptanes solution was charged to the reactor after thecatalyst charge but before the isobutane (reactor solvent) charge topurge feedstock poisons.

Run 4: 0.080 g of Product I (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 6.0 ml of a 1M TEA in hexanessolution was added and the solution stirred for 16 hours. The formationof a brown solution and the complete dissolution of Product I resultedimmediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.50 g) wasadded to the solution and stirred for an additional 16 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then rinsed twice pentane. 1.1988 g ofthe catalyst was charged directly to the reactor for polymerization.

Run 5: 0.079 g of Product II (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 2.0 ml of a 1.9M TEA in toluenesolution was added to the solution and stirred for 8 hours. Theformation of a brown solution and the complete dissolution of Product IIresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4)(0.50 g) was added to the solution and stirred for an additional 16hours. The supported catalyst was filtered from the solution as a brownsolid, rinsed twice with toluene, and then twice with pentane. 0.4829 gof the catalyst was charged directly to the reactor for polymerization.

Run 6: 0.071 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF, wasslurried with 15 ml toluene at ambient temperature. 2.0 ml of a 1M TEAin hexanes solution was added to the solution and stirred for 1 hour.The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. SiO₂ (2.52 g) wasadded to the solution and stirred for an additional 2 minutes. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice with pentane. All of thecatalyst was charged directly to the reactor for polymerization.

Run 7: 0.103 g of Product II (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 1.0 ml of a 1.9M TEA in toluenesolution was added to the solution and stirred for 10 minutes. Theformation of a brown solution and the complete dissolution of Product IIresulted immediately upon TEA addition. Al₂ O₃ (2.27 g) was added to thesolution and stirred for an additional 2 minutes. The supported catalystwas filtered from the solution as a brown solid, rinsed twice withtoluene, and then twice with pentane. 1.2926 g of the catalyst wascharged directly to the reactor for polymerization.

Run 8: 0.120 g of Product I (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 2.0 ml of a 1M TEA in hexanessolution was added to the solution and stirred for 2 days. The formationof a brown solution and the complete dissolution of Product I resultedimmediately upon TEA addition. SiO₂ (1.0 g) was added to the solutionand stirred for an additional 3 weeks. The supported catalyst wasfiltered from the solution as a brown solid, rinsed twice with toluene,and then twice with pentane. All of the catalyst was charged directly tothe reactor for polymerization.

Run 9: 0.106 g of Product III (prepared in THF solvent) was slurriedwith 15 ml toluene at ambient temperature. 2.5 ml of a 1.9M TEA intoluene solution was added to the solution and stirred for 2 hours. Theformation of a brown solution and the complete dissolution of ProductIII resulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4)(0.65 g) was added to the solution and stirred for an additional 2hours. The supported catalyst was filtered from the solution as a brownsolid, rinsed twice with toluene, and then twice with pentane. All ofthe catalyst was charged directly to the reactor for polymerization. 1.5ml of a 1.0% TEA in pentane solution was charged to the reactor afterthe catalyst charge but before the isobutane (reactor solvent) charge topurge feedstock poisons.

Run 10: 0.030 g of Product V (prepared in THF solvent) which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF wasslurried with 15 ml toluene at ambient temperature. 3.0 ml of a 1M TEAin hexanes solution was added to the solution and stirred for 16 hours.The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. AlPO₄ (P/Al=0.9) (2.0g) was added to the solution and stirred for an additional 16 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice with pentane. 0.322/g ofcatalyst was charged directly to the reactor for polymerization.

Run 11: 0.067 g of Product V (prepared in THF solvent) was slurried with15 ml pentane at ambient temperature. 4.0 ml of a 1M TEA in hexanessolution was added to the solution and stirred for 24 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.0g) was added to the solution and stirred for an additional 24 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with pentane. All of the catalyst was charged directly tothe reactor for polymerization. 3.0 ml of a 0.5% TEA in heptanessolution was charged to the reactor after the catalyst charge but beforethe isobutane (reactor solvent) charge to purge feedstock poisons.

Run 12: 0.073 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF, wasslurried with 15 ml toluene at ambient temperature. 6.0 ml of a 1M TEAin hexanes solution was added and the solution stirred for 24 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. P/SiO₂ (7.0 g) was added to thesolution and stirred for an additional 24 hours which nearly decolorizedit. The supported catalyst was filtered from the solution as a brownsolid, rinsed twice with toluene, and then twice with pentane. 2.85 g ofcatalyst was charged directly to the reactor for polymerization.

Run 13: 0.125 g or Product II was slurried with 15 ml diethylbenzene atambient temperature. 9.0 ml of a 1M TEA in hexanes solution was added tothe solution and stirred for 8 hours. The formation of a brown solutionand the complete dissolution of Product II resulted immediately upon TEAaddition. F/Al₂ O₃ (2.0 g) was added to the solution and stirred for anadditional 12 hours. The supported catalyst was filtered from thesolution as a brown solid, rinsed twice with toluene, and then twicewith pentane. 0.5477 g of catalyst was charged directly to the reactorfor polymerization.

Run 14: 0.125 g of Product VI was slurried with 15 ml toluene at ambienttemperature. 1.5 ml of a 1M TEA in hexanes solution was added and thesolution stirred for 10 minutes. The formation of a red/brown solutionand the complete dissolution of Product VI resulted immediately upon TEAaddition. SiO₂ (2.0 g) was added to the solution and stirred for anadditional 1 minute which nearly decolorized it. The supported silicacatalyst was filtered from the solution as a red/brown solid, rinsedtwice with toluene, and then twice with pentane. All of the catalyst wascharged directly to the reactor for polymerization.

Run 15: 0.30 g of Product V (prepared in DME solvent) was dissolved with15 ml of dimethoxyethane forming a green solution. This solution wasthen mixed with 0.6 g of AlPO₄ (P/Al₄ mole ratio=0.4) (2.00 g) and themixture was stirred 1 hour. The green supported material was filteredfrom the solution, rinsed with dimethoxyethane and dried with a nitrogenpurge at 90° C. This material was then stirred with 15 ml of toluene and3 ml of triethylaluminum (Aldrich 1.0M, hexanes) for an additional 3hours. The brown supported catalyst was collected by filtration, rinsedwith pentane, and dried under vacuum. 0.4609 g of the catalyst wascharged directly to the reactor for polymerization. 3.0 ml of a 0.5% TEAin heptanes solution was charged to the reactor after the catalystcharge but before the isobutane (reactor solvent) charge to purgefeedstock poisons.

Run 16: 0.058 g of Product V (prepared in THF solvent) which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF wasslurried with 15 ml benzene at ambient temperature. 4.0 ml of a 1M TEAin hexanes solution was added and the solution stirred for 2 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.0g) was added to the solution and stirred for 1 hour. The supportedcatalyst was filtered from the solution as a brown solid, rinsed twicewith benzene, and then twice with pentane. All of the catalyst wascharged directly to the reactor for polymerization. 3.0 ml of a 0.5% TEAin heptanes solution was charged to the reactor after the catalystcharge but before the isobutane (reactor solvent) charge to purgefeedstock poisons.

Run 17: 0.1610 g of Product I was charged directly to the reactor at 90°C. The reactor was charged with 1 liter isobutane and pressurized to 550psig with ethylene. No ethylene consumption was detected, therefore 50psig of dihydrogen (H₂) was charged to the reactor which did notinitiate ethylene consumption. Ethylene consumption was initiated after2.0 ml of 1M TEA in hexanes solution was charged.

Run 18: 0.3528 g of Product VI was charged directly to the reactor at90° C. The reactor was charged with 1 liter isobutane and pressurized to550 psig with ethylene. No ethylene consumption was detected, therefore2.0 ml of a 1M TEA in hexanes solution was charged which did initiateethylene consumption.

Run 19: 0.3482 g of Product VI was charged directly to the reactor at90° C. The reactor was also charged with 2.0 ml of a 1M TEA in hexanessolution prior to a 1 liter isobutane charge. The reactor was thenpressurized to 550 psig with ethylene. No ethylene consumption wasdetected, therefore 30 psi of dihydrogen was charged to the reactorwhich initiated ethylene consumption.

Run 20: 0.202 g of Product V (prepared in dimethoxyethane (DME)solvent), 6.0 ml of a 1.9M TEA in toluene solution, and 2.0 g of AlPO₄(P/Al mole ratio=0.4) were mixed with 15 ml toluene at ambienttemperature. The formation of a brown solution and the completedissolution of Product V resulted immediately upon mixing. The brownsolution was stirred for 48 hours. The supported catalyst was filteredfrom the solution as a brown solid, rinsed twice with toluene, and thentwice with pentane. 0.0671 g of the catalyst was charged directly to thereactor for polymerization. 1.0 ml of a 0.5% TEA in heptanes solutionwas charged to the reactor after the catalyst charge but before theisobutane (reactor solvent) charge to purge feedstock poisons.

The data in Table XVI show that the inventive chromium compounds can beused either supported (Runs 1-16, 20) or unsupported (Runs 17-19) topolymerize and/or trimerize olefins. Furthermore, conditions can bevaried to increase the amount of trimer product (Runs 1-5 and 9) or tohave a higher yield of solid, or polymer, product (Runs 6, 7, and 13).Runs 1, 3, and 20 demonstrate that high activities are attainable.

                                      TABLE XVI                                   __________________________________________________________________________    Run.sup.a                                                                        Catalyst   Support.sup.b                                                                       Products    Activity.sup.c                                __________________________________________________________________________     1 (V)/TEA/Toluene                                                                          AlPO.sub.4                                                                          98.4% liquids, 1.6% solids                                                                1030                                           2 (V)/TEA/Diethylbenzene                                                                   AlPO.sub.4                                                                          99.4% liquids, 0.6% solids                                                                730                                            3 (V)/TEA/Toluene                                                                          AlPO.sub.4                                                                          99.4% liquids, 0.6% solids                                                                1450                                           4 (I)/TEA/Toluene                                                                          AlPO.sub.4                                                                          98.6% liquids, 1.4% solids                                                                360.sup.d                                      5 (II)/TEA/Toluene                                                                         AlPO.sub.4                                                                          98.2% liquids, 1.8% solids                                                                580                                            6 (V)/TEA/Toluene                                                                          SiO.sub.2                                                                           89.0% liquids, 11.0% solids                                                               80                                             7 (II)/TEA/Toluene                                                                         Al.sub.2 O.sub.3                                                                    55.8% liquids, 44.2% solids                                                               50                                             8 (I)/TEA/Toluene                                                                          SiO.sub.2                                                                           93.3% liquids, 6.7% solids                                                                400                                            9 (III)/TEA/Toluene                                                                        AlPO.sub.4                                                                          99.8% liquids, 0.2% solids                                                                100                                           10 (V)/TEA/Toluene                                                                          AlPO.sub.4 (.9)                                                                     96.8% liquids, 3.2% solids                                                                930                                           11 (V)/TEA/Pentane                                                                          AlPO.sub.4                                                                          (trace) liquids, (trace) solids                                                           unreactive                                    12 (V)/TEA/Toluene                                                                          P/SiO.sub.2                                                                         98.1% liquids, 1.9% solids                                                                90                                            13 (II)/TEA/Diethylbenzene                                                                  F/Al.sub.2 O.sub.3                                                                  88.0% liquids, 12.0% solids                                                               300                                           14 (VI)/TEA/Toluene                                                                         SiO.sub.2                                                                           94.3% liquids, 5.7% solids                                                                40                                            15 (V)/DME    AlPO.sub.4                                                                          98.0% liquids, 2.0% solids                                                                550                                           16 (V)/TEA/Benzene                                                                          AlPO.sub.4                                                                          99.1% liquids, 0.9% solids                                                                500                                           17 (I)/TEA    unsupported                                                                         98.3% liquids, 1.7% solids                                                                340                                           18 (VI)/TEA   unsupported                                                                         99.4% liquids, 0.6% solids                                                                180                                           19 (VI)/TEA   unsupported                                                                         98.1% liquids, 1.9% solids                                                                230                                           20 (V)/TEA/Toluene                                                                          AlPO.sub.4                                                                          99.5% liquids, 0.5% solids                                                                2760                                          __________________________________________________________________________     .sup.a All runs were made at 90° C., isobutane solvent, 550 psi        total pressure.                                                               .sup.b P/Al mole ratio = 0.4; except Run 10 whereby P/Al mole ratio = 0.9     .sup.c Grams product/grams catalyst/hour based on 30 min. run times.          .sup.d Believed to be lower than actual due to experimental error; actual     value believe to be near 2000.                                           

                  TABLE XVII                                                      ______________________________________                                                    1-                                                                            hex-                                                              Run  C4     ene    C6    C8   C10   C12  C14  C16-C28                         ______________________________________                                         1   0.05   81.92  7.76  0.49 9.12  0.09 0.52 .05                              2   0.10   78.80  7.49  0.58 11.36 0.10 1.01 .56                              3   0.06   82.19  7.68  0.45 8.85  0.08 0.58 .11                              5   0.10   83.40  7.08  0.62 8.08  0.05 0.42 .25                              6   0.55   78.70  5.52  1.84 11.24 0.42 1.26 .47                             16   0.06   72.85  13.61 0.31 12.06 0.09 0.93 .09                             19   6.03   71.66  6.09  3.61 9.42  1.17 1.41 .61                             ______________________________________                                    

EXAMPLE IX

Single crystal x-ray structures were obtained for Cr(NC₄ H₄)₃ Cl(O₂ C₂H₄ (CH₃)₂)₃ Na, shown in FIGS. 7 and 8, and Cr(NC₄ H₄)₃ Cl(O₂ C₂ H₄(CH₃)₂), and shown in FIG. 9. These crystals were obtained in accordancewith the procedure given in Example III. However, x-ray quality crystalswere obtained after the dark green, filtered solution was maintained atambient temperature and pressure under an inert atmosphere, nitrogen,for a time of about 2 days. Analysis calculated for C₂₄ H₄₂ N₃ O₆CrNaCl: C, 49.78; H, 7.31; N, 7.26% by weight. Found: C, 49.80; H 7.39;N, 7.18% by weight.

The description of the single-crystal sample and mounting used for datacollection are as follows:

Color: Green/black

Shape: Rectangular parallelepiped

Dimensions: 0.44×0.62×0.62 mm

Crystal Mount: Crystal was glued to the inside of a thin-walled glasscapillary and sealed under N₂.

Crystal Orientation: Crystal was oriented with its longer edges nearlyparallel to the phi axis of the diffractometer.

Width at Half-height from ω Scans: 0.38°

The space group and cell data are as follows:

Crystal System: Monoclinic

Space Group and Number: P2₁ /c - C_(2h) (No. 14)

Number of Computer-Centered Reflections Used in the Least-SquaresRefinement of the Cell Dimensions:

15 20>25° °C=20±1

Lattice Constants with esd's:

    ______________________________________                                        a = 8.135(2)Å                                                                          α = 90.00°                                                                    V = 3027(1)Å.sup.3                              b = 22.337(5)Å                                                                         β = 91.67(2)°                                                                  Z = 4                                               c = 16.667(4)Å                                                                         γ = 90.00°                                                                    λ = 0.71073Å                             ______________________________________                                    

Molecular Weight: 579.05 amu

Calculated Density: 1.271 g/cm⁻³

Linear Absorption Coefficient: 0.51 mm⁻¹

Tables XVIII-XXII list the resultant parameters used to generate themolecular structures shown in FIGS. 7 and 8.

                  TABLE XVIII                                                     ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in                                   Crystalline  Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4          (CH.sub.3).sub.2).sub.3 Na!.sup.a                                                                         Equivalent Isotropic                              Atom   Fractional Coordinates                                                                             Thermal Parameter,                                Type.sup.b                                                                           10.sup.4 x                                                                              10.sup.4 y                                                                              10.sup.4 z                                                                           B, Å.sup.2 × 10.sup.c             ______________________________________                                        Cr     -1030(1)  559(1)    3005(1)                                                                              30(1)                                       Cl     135(1)    -26(1)    1981(1)                                                                              41(1)                                       Na     -2167(2)  -1011(1)  1832(1)                                                                              46(1)                                       N.sub.1                                                                              -3062(4)  65(2)     2907(2)                                                                              35(1)                                       C.sub.11                                                                             -4107(5)  63(2)     2251(3)                                                                              40(1)                                       C.sub.12                                                                             -5189(5)  -409(2)   2291(3)                                                                              51(1)                                       C.sub.13                                                                             -4810(5)  -713(2)   2998(3)                                                                              51(1)                                       C.sub.14                                                                             -3512(5)  -414(2)   3361(3)                                                                              46(1)                                       N.sub.2                                                                              -1817(4)  1027(2)   3950(2)                                                                              37(1)                                       C.sub.21                                                                             -1188(6)  1558(2)   4234(3)                                                                              47(1)                                       C.sub.22                                                                             -2205(7)  1790(2)   4799(3)                                                                              60(2)                                       C.sub.23                                                                             -3499(7)  1398(2)   4874(3)                                                                              60(2)                                       C.sub.24                                                                             -3248(5)  934(2)    4349(2)                                                                              43(1)                                       N.sub.3                                                                              -1892(4)  1185(2)   2260(2)                                                                              35(1)                                       C.sub.31                                                                             -3100(5)  1588(2)   2434(3)                                                                              41(1)                                       C.sub.32                                                                             -3573(6)  1901(2)   1757(3)                                                                              53(1)                                       C.sub.33                                                                             -2631(6)  1686(2)   1130(3)                                                                              51(1)                                       C.sub.34                                                                             -1620(6)  1249(2)   1453(3)                                                                              46(1)                                       O.sub.1a                                                                             1317(3)   971(1)    3154(2)                                                                              40(1)                                       O.sub.2a                                                                             153(3)    -12(1)    3878(2)                                                                              40(1)                                       C.sub.1a                                                                             2459(5)   631(2)    3651(3)                                                                              53(1)                                       C.sub.2a                                                                             1443(6)   329(2)    4268(3)                                                                              53(1)                                       C.sub.3a                                                                             2156(6)   1247(2)   2495(3)                                                                              58(2)                                       C.sub.4a                                                                             653(6)    -625(2)   3733(3)                                                                              49(1)                                       O.sub.1b                                                                             -2558(4)  -783(2)   398(2) 62(1)                                       O.sub.2b                                                                             -3877(5)  -1772(2)  1111(2)                                                                              76(1)                                       C.sub.1b                                                                             -3618(9)  -1166(3)  -25(4) 89(2)                                       C.sub.2b                                                                             -3627(9)  -1765(3)  302(4) 83(2)                                       C.sub.3b                                                                             -2410(8)  -207(3)   61(4)  79(2)                                       C.sub.4b                                                                             -4149(9)  -2328(3)  1440(5)                                                                              106(3)                                      O.sub.1c                                                                             -1334(4)  -1823(2)  2911(2)                                                                              65(1)                                       O.sub.2c                                                                             235(5)    -1589(2)  1529(3)                                                                              87(2)                                       C.sub.1c                                                                             71(7)     -2144(3)  2724(4)                                                                              83(2)                                       C.sub.2c                                                                             951(8)    -1913(4)  2067(4)                                                                              107(3)                                      C.sub.3c                                                                             -2090(8)  -2017(3)  3614(4)                                                                              83(2)                                       C.sub.4c                                                                             1224(8)   -1393(3)  900(4) 88(2)                                       ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 7                             .sup.c This is onethird of the trace of the orthogonalized B.sub.ij           tensor.                                                                  

                  TABLE XIX                                                       ______________________________________                                        Anisotropic Thermal Parameters for Nonhydrogen Atoms                          in Crystalline                                                                 Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4 (CH.sub.3).sub.2)    .sub.3 Na!.sup.a,b                                                            Atom  Anisotropic Thermal Parameter (λ.sup.2 × 10)               Type.sup.c                                                                          B.sub.11 B.sub.22                                                                              B.sub.33                                                                             B.sub.12                                                                            B.sub.13                                                                            B.sub.23                            ______________________________________                                        Cr    28(1)    31(1)   30(1)  2(1)  -0(1) -2(1)                               Cl    39(1)    43(1)   41(1)  2(1)  5(1)  -9(1)                               Na    47(1)    48(1)   44(1)  0(1)  3(1)  -4(1)                               N.sub.1                                                                             31(1)    39(2)   35(2)  0(1)  2(1)  -3(1)                               C.sub.11                                                                            31(2)    47(2)   41(2)  0(2)  -1(2) -7(2)                               C.sub.12                                                                            33(2)    59(3)   61(3)  -3(2) -4(2) -16(2)                              C.sub.13                                                                            35(2)    39(2)   79(3)  -6(2) 8(2)  3(2)                                C.sub.14                                                                            39(2)    45(2)   54(2)  1(2)  2(2)  10(2)                               N.sub.2                                                                             36(2)    38(2)   36(2)  7(1)  -3(1) -8(1)                               C.sub.21                                                                            55(2)    38(2)   47(2)  9(2)  -6(2) -5(2)                               C.sub.22                                                                            88(3)    46(3)   44(2)  32(2) -9(2) -12(2)                              C.sub.23                                                                            65(3)    74(3)   42(2)  32(2) 7(2)  0(2)                                C.sub.24                                                                            37(2)    55(2)   37(2)  14(2) -0(2) 1(2)                                N.sub.3                                                                             38(2)    35(2)   32(2)  3(1)  0(1)  -0(1)                               C.sub.31                                                                            35(2)    43(2)   43(2)  6(2)  -3(2) 1(2)                                C.sub.32                                                                            52(2)    47(2)   58(3)  8(2)  -11(2)                                                                              6(2)                                C.sub.33                                                                            62(3)    51(3)   39(2)  -2(2) -8(2) 12(2)                               C.sub.34                                                                            52(2)    45(2)   40(2)  -1(2) 2(2)  2(2)                                O.sub.1a                                                                            32(1)    40(1)   50(2)  -1(1) -3(1) -5(1)                               O.sub.2a                                                                            40(1)    38(1)   41(1)  6(1)  -7(1) -1(1)                               C.sub.1a                                                                            33(2)    50(3)   73(3)  4(2)  -13(2)                                                                              -10(2)                              C.sub.2a                                                                            53(2)    55(3)   51(2)  10(2) -24(2)                                                                              -10(2)                              C.sub.3a                                                                            45(2)    53(3)   76(3)  -15(2)                                                                              8(2)  -5(3)                               C.sub.4a                                                                            50(2)    40(2)   58(3)  12(2) -8(2) -1(2)                               O.sub.1b                                                                            76(2)    63(2)   47(2)  -14(2)                                                                              -5(2) 1(2)                                O.sub.2b                                                                            101(3)   62(2)   63(2)  -28(2)                                                                              -5(2) -2(2)                               C.sub.1b                                                                            120(5)   91(4)   56(3)  -29(4)                                                                              -25(3)                                                                              -3(3)                               C.sub.2b                                                                            116(5)   64(3)   68(4)  -18(3)                                                                              -24(3)                                                                              -12(3)                              C.sub.3b                                                                            81(4)    84(4)   72(4)  -9(3) -1(3) 19(3)                               C.sub.4b                                                                            118(5)   84(4)   113(5) -5l(4)                                                                              -38(4)                                                                              29(4)                               O.sub.1c                                                                            61(2)    64(2)   70(2)  8(2)  0(2)  4(2)                                O.sub.2c                                                                            74(2)    76(3)   112(3) 29(2) 31(2) 30(2)                               C.sub.1c                                                                            73(3)    65(3)   113(5) 23(3) 9(3)  25(3)                               C.sub.2c                                                                            83(4)    143(6)  96(5)  61(4) 24(4) 14(5)                               C.sub.3c                                                                            84(4)    64(3)   101(5) -8(3) 3(4)  16(3)                               C.sub.4c                                                                            77(4)    98(5)   90(5)  13(3) 29(3)                                     5(4)                                                                          ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b The form of the anisotropic thermal parameter is given in referenc     8 on page 6 of the crystal structure analysis report.                         .sup.c Atoms are labeled in agreement with FIG. 7.                       

                  TABLE XX                                                        ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in Crystalline                           Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4 (CH.sub.3).sub.2)    .sub.3 Na!.sup.a                                                              Atom     Fractional Coordinates                                               Type.sup.b                                                                             10.sup.4 x    10.sup.4 y                                                                            10.sup.4 z                                     ______________________________________                                        H.sub.11 -4089            350  1823                                           H.sub.12 -6043          -509   1905                                           H.sub.13 -5349         -1064   3195                                           H.sub.14 -2993          -526   3863                                           H.sub.21  -188           1740  4063                                           H.sub.22 -2044           2158  5089                                           H.sub.23 -4404           1441  5226                                           H.sub.24 -3967            597  4273                                           H.sub.31 -3554           1644  2954                                           H.sub.32 -4392           2210  1720                                           H.sub.33 -2680           1817   581                                           H.sub.34  -840           1021  1159                                           H.sub.1aa                                                                                3041           339  3336                                           H.sub.1ab                                                                                3254           892  3906                                           H.sub.2aa                                                                                 967           626  4606                                           H.sub.2ab                                                                                2127           67   4588                                           H.sub.3aa                                                                                1391          1487  2185                                           H.sub.3ab                                                                                2589           938  2162                                           H.sub.3ac                                                                                3040          1495  2696                                           H.sub.4aa                                                                               -256          -834   3484                                           H.sub.4ab                                                                                 926         -806   4242                                           H.sub.4ac                                                                                1586         -646   3395                                           H.sub.1ba                                                                              -4712         -1006    -11                                           H.sub.1bb                                                                              -3277         -1186   -570                                           H.sub.2ba                                                                              -2588         -1951    204                                           H.sub.2bb                                                                              -4492         -1988    37                                            H.sub.3ba                                                                              -1696            26    407                                           H.sub.3bb                                                                              -3461          -14      7                                            H.sub.3bc                                                                              -1935          -243   -458                                           H.sub.4ba                                                                              -4380         -2289   2000                                           H.sub.4bb                                                                              -3108         -2524   1385                                           H.sub.4bc                                                                              -4998         -2561   1178                                           H.sub.1ca                                                                                 795        -2146   3189                                           H.sub.1cb                                                                               -255         -2547   2596                                           H.sub.2ca                                                                                1398        -2252   1795                                           H.sub.2cb                                                                                1831        -1676   2294                                           H.sub.3ca                                                                              -3168         -1848   3661                                           H.sub.3cb                                                                              -1397         -1884   4055                                           H.sub.3cc                                                                              -2164         -2446   3624                                           H.sub.4ca                                                                                 456        -1357    454                                           H.sub.4cb                                                                                2033        -1690    780                                           H.sub.4cc                                                                                1756        -1015    996                                           ______________________________________                                         .sup.a The 6 methyl groups were refined as rigid rotors with                  sp.sup.3hybridized geometry and C--H bond lengths of 0.96Å. The           initial orientation of each methyl group was determined from difference       Fourier positions for the hydrogen atoms. The final orientation of each       methyl group was determined by three rotational parameters. The refined       positions for the rigid rotor methyl groups gave O--C--H angles which         ranged from 103° to 115°. The remaining hydrogen atoms were     included in the structure factor calculations as idealized atoms (assumin     sp.sup.2 or sp.sup.3hybridization of the carbon atoms and a C--H bond         length of 0.96Å) "riding" on their respective carbon atoms. The           isotropic thermal parameter of each hydrogen was fixed at 1.2 times the       equivalent isotropic thermal parameter of the carbon atom to which it is      covalently bonded.                                                            .sup.b Hydrogens are labeled with the same subscripts as their carbon         atoms with an additional literal subscript (a , b or c) where necessary t     distinguish between hydrogen atoms bonded to the same carbon.            

                  TABLE XXI                                                       ______________________________________                                        Bond Lengths Involving Nonhydrogen Atoms in                                   Crystalline  Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4          (CH.sub.3).sub.2).sub.3 Na!.sup.a                                             Type.sup.b                                                                             Length, Å                                                                              Type.sup.b                                                                             Length, Å                                  ______________________________________                                        Cr--Cl   2.369(1)     Cr--N.sub.1                                                                            1.990(3)                                                             Cr--N.sub.2                                                                            2.010(3)                                       Cr--O.sub.1a                                                                           2.128(3)     Cr--N.sub.3                                                                            1.986(3)                                       Cr--O.sub.2a                                                                           2.142(3)                                                             N.sub.1 --C.sub.11                                                                     1.365(5)     C.sub.11 --C.sub.12                                                                    1.376(6)                                       N.sub.1 --C.sub.14                                                                     1.366(6)     C.sub.12 --C.sub.13                                                                    1.386(7)                                       N.sub.2 --C.sub.21                                                                     1.370(6)     C.sub.13 --C.sub.14                                                                    1.376(6)                                       N.sub.2 --C.sub.24                                                                     1.374(5)     C.sub.21 --C.sub.22                                                                    1.373(7)                                       N.sub.3 --C.sub.31                                                                     1.370(5)     C.sub.22 --C.sub.23                                                                    1.377(8)                                       N.sub.3 --C.sub.34                                                                     1.376(6)     C.sub.23 --C.sub.24                                                                    1.375(7)                                                             C.sub.31 --C.sub.32                                                                    1.373(7)                                       O.sub.1a --C.sub.1a                                                                    1.443(5)     C.sub.32 --C.sub.33                                                                    1.399(7)                                       O.sub.1a --C.sub.3a                                                                    1.448(6)     C.sub.33 --C.sub.34                                                                    1.375(7)                                       O.sub.2a --C.sub.2a                                                                    1.437(5)                                                             O.sub.2a --C.sub.4a                                                                    1.450(5)     C.sub.1a --C.sub.2a                                                                    1.498(7)                                       O.sub.1b --C.sub.1b                                                                    1.391(8)     C.sub.1b --C.sub.2b                                                                    1.445(9)                                       O.sub.1b --C.sub.3b                                                                    1.410(7)     C.sub.1c --C.sub.2c                                                                     1.422(10)                                     O.sub.2b --C.sub.2b                                                                    1.370(7)                                                             O.sub.2b --C.sub.4b                                                                    1.379(8)     Na . . . Cr                                                                            4.108(2)                                       O.sub.1c --C.sub.1c                                                                    1.392(7)                                                             O.sub.1c --C.sub.3c                                                                    1.408(8)     Na--Cl   2.896(2)                                       O.sub.2c --C.sub.2c                                                                    1.278(9)                                                             O.sub.2c --C.sub.4c                                                                    1.409(8)     Na--N.sub.1                                                                            3.098(4)                                       Na--C.sub.11                                                                           2.967(5)     Na--O.sub.1b                                                                           2.454(4)                                       Na--C.sub.12                                                                           2.924(5)     Na--O.sub.2b                                                                           2.483(4)                                       Na--C.sub.13                                                                           3.015(5)     Na--O.sub.1c                                                                           2.629(5)                                       Na--C.sub.14                                                                           3.104(5)     Na--O.sub.2c                                                                           2.408(5)                                       Na--C.sub.g1.sup.c                                                                      2.788(--)                                                           ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 7.                            .sup.c The symbol C.sub.g1 is used to designate the center of gravity for     the five--membered ring containing N.sub.1, C.sub.11, C.sub.12, C.sub.13,     and C.sub.14 ; this value is therefore listed without an estimated            standard deviation.                                                      

                  TABLE XXII                                                      ______________________________________                                        Bond Angles Involving Nonhydrogen Atoms in                                    Crystalline  Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4          (CH.sub.3).sub.2).sub.3 Na!.sup.a                                             Type.sup.b                                                                             Angle, deg.  Type.sup.b                                                                              Angle, deg.                                   ______________________________________                                        ClCrN.sub.1                                                                             89.1(1)     ClCrN.sub.2                                                                             173.9(1)                                      N.sub.1 CrN.sub.2                                                                       94.0(1)     ClCrN.sub.3                                                                              94.5(1)                                      N.sub.1 CrN.sub.3                                                                       93.5(1)     N.sub.2 CrN.sub.3                                                                        90.5(1)                                      ClCrO.sub.1a                                                                            86.9(1)     N.sub.1 CrO.sub.1a                                                                      171.9(1)                                      N.sub.2 CrO.sub.1a                                                                      89.4(1)     N.sub.3 CrO.sub.1a                                                                       93.8(1)                                      ClCrO.sub.2a                                                                            88.9(1)     N.sub.1 CrO.sub.2a                                                                       94.7(1)                                      N.sub.2 CrO.sub.2a                                                                      85.7(1)     N.sub.3 CrO.sub.2a                                                                      171.2(1)                                      O.sub.1a CrO.sub.2a                                                                     78.2(1)                                                             CrN.sub.1 C.sub.11                                                                     124.4(3)     C.sub.11 N.sub.1 C.sub.14                                                               105.7(3)                                      CrN.sub.1 C.sub.14                                                                     128.6(3)     C.sub.21 N.sub.2 C.sub.24                                                               106.1(4)                                      CrN.sub.2 C.sub.21                                                                     126.6(3)     C.sub.31 N.sub.3 C.sub.34                                                               106.0(3)                                      CrN.sub.2 C.sub.24                                                                     126.5(3)                                                             CrN.sub.3 C.sub.31                                                                     125.0(3)     CrO.sub.1a C.sub.1a                                                                     113.5(2)                                      CrN.sub.3 C.sub.34                                                                     128.3(3)     CrO.sub.1a C.sub.3a                                                                     122.5(3)                                                            C.sub.1a O.sub.1a C.sub.3a                                                              110.5(3)                                      N.sub.1 C.sub.11 C.sub.12                                                              110.3(4)     CrO.sub.2a C.sub.2a                                                                     107.4(2)                                      C.sub.11 C.sub.12 C.sub.13                                                             106.9(4)     CrO.sub.2a C.sub.4a                                                                     124.9(3)                                      C.sub.12 C.sub.13 C.sub.14                                                             106.5(4)     C.sub.2a O.sub.2a C.sub.4a                                                              111.8(3)                                      N.sub.1 C.sub.14 C.sub.13                                                              110.6(4)     C.sub.1b O.sub.1b C.sub.3b                                                              114.7(4)                                      N.sub.2 C.sub.21 C.sub.22                                                              109.7(4)     C.sub.2b O.sub.2b C.sub.4b                                                              115.6(5)                                      C.sub.21 C.sub.22 C.sub.23                                                             107.4(4)     C.sub.1c O.sub.1c C.sub.3c                                                              114.2(5)                                      C.sub.22 C.sub.23 C.sub.24                                                             107.1(4)     C.sub.2c O.sub.2c C.sub.4c                                                              116.0(5)                                      N.sub.2 C.sub.24 C.sub.23                                                              109.7(4)                                                             N.sub.3 C.sub.31 C.sub.32                                                              110.3(4)     O.sub.1a C.sub.1a C.sub.2a                                                              105.8(3)                                      C.sub.31 C.sub.32 C.sub.33                                                             107.0(4)     O.sub.2a C.sub.2a C.sub.1a                                                              109.8(4)                                      C.sub.32 C.sub.33 C.sub.34                                                             106.6(4)     O.sub.1b C.sub.1b C.sub.2b                                                              112.8(5)                                      N.sub.3 C.sub.34 C.sub.33                                                              110.2(4)     O.sub.2b C.sub.2b C.sub.1b                                                              112.6(5)                                                            O.sub.1c C.sub.1c C.sub.2c                                                              114.9(6)                                      ClNaC.sub.g1.sup.c                                                                      83.6(--)    O.sub.2c C.sub.2c C.sub.1c                                                              121.1(6)                                      ClNaO.sub.1b                                                                            89.5(1)     C.sub.g1 NaO.sub.1b.sup.c                                                                111.1(--)                                    ClNaO.sub.2b                                                                           156.0(1)     C.sub.g1 NaO.sub.2b.sup.c                                                                110.2(--)                                    ClNaO.sub.1c                                                                           108.2(1)     C.sub.g1 NaO.sub.1c.sup.c                                                                99.4(--)                                     ClNaO.sub.2c                                                                            84.2(1)     C.sub.g1 NaO.sub.1c.sup.c                                                                155.9(--)                                    ClNaN.sub.1                                                                             61.5(1)     O.sub.1b NaO.sub.2b                                                                      67.4(2)                                      ClNaC.sub.11                                                                            73.3(2)     O.sub.1b NaO.sub.1c                                                                     146.4(2)                                      ClNaC.sub.12                                                                           100.0(2)     O.sub.1b NaO.sub.2c                                                                      89.4(2)                                      ClNaC.sub.13                                                                           104.4(2)     O.sub.2b NaO.sub.1c                                                                      89.3(2)                                      ClNaC.sub.14                                                                            81.1(2)     O.sub.2b NaO.sub.2c                                                                      65.1(2)                                                            O.sub.1c NaO.sub.2c                                     N.sub.1 NaC.sub.11                                                                      25.9(2)                                                             N.sub.1 NaC.sub.14                                                                      25.5(2)     N.sub.1 NaC.sub.12                                                                       43.8(2)                                      C.sub.11 NaC.sub.12                                                                     27.0(2)     N.sub.1 NaC.sub.13                                                                       43.2(2)                                      C.sub.13 NaC.sub.13                                                                     26.9(2)     C.sub.11 NaC.sub.13                                                                      43.5(2)                                      C.sub.13 NaC.sub.14                                                                     25.9(2)     C.sub.12 NaC.sub.14                                                                      42.9(2)                                                            C.sub.11 NaC.sub.14                                                                      41.9(2)                                      ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 7.                            .sup.c The symbol C.sub.g1 is used to designate the center of gravity for     the fivemembered ring containing N.sub.1, C.sub.11, C.sub.12, C.sub.13,       and C.sub.14 ; this value is therefore listed without an estimated            standard deviation.                                                      

EXAMPLE X Run 1001

0.14 g (0.29 mmol) of chromium (III) 2-ethylhexanoate (CrEH₃), Cr(C₈ H₁₅O₂)₃ !, was weighed into a 25 ml pressure tube. The tube was capped witha self sealing crown cap. 0.062 ml (0.89 mmol) pyrrole (PyH), C₄ NH₅ !and cyclohexane, used as a diluent, were added via syringe to form asolution, which was about 8 ml total volume.

0.9 ml of a 1.1M solution (0.99 mmol) of triethylaluminum (TEA), Al(C₂H₅)₃ !, in heptane and a 0.9 ml aliquot of the CrEH₃ /PyH solution wereadded under a counterflow of ethylene (CP grade) to a 1 liter autoclavereactor, containing 300 mL cyclohexane, to form a catalyst system. Thereactor was sealed and ethylene addition stopped until the reactortemperature reached a reaction temperature of 80° C. The ethylenepressure was increased to a total reactor pressure of 550 psig. Ethylenewas then fed on demand for a 30 minute run time. At the end of the run,a sample of the liquid reaction product mixture was taken and analyzedvia capillary gas chromatography. The remaining reaction product mixturewas evaporated and the amount of solid product was determined. Theresults are summarized below in Table XXIII.

Run 1002

The procedure described in Run 1001 was followed except 8 ml of a 1.1Msolution (8.8 mmol) of TEA in heptane was added directly to the CrEH₃/PyH solution to form a solution (10 ml total volume) and not to thereactor. A 0.7 ml aliquot of the CrEH₃ /PyH/TEA solution was added tothe autoclave reactor. No additional TEA was introduced into thereactor. The results are summarized below in Table XXIII.

Run 1003

The procedure described in Run 1002 was followed except 0.10 g (0.29mmol) chromium (III) acetylacetonate (Cracac₃), Cr(C₅ H₇ O₂)₃ !, wassubstituted for CrEH₃ and 6 ml of a 1.1M solution TEA (6.6 mmol) inheptane was used in the formation of a Cracac₃ /PyH/TEA solution (8 mltotal volume). A 1.4 ml aliquot of the Cracac₃ /PyH/TEA solution wasadded to the autoclave reactor. The results are summarized below inTable XXIII.

Run 1004

The procedure described in Run 1001 was followed except 0.9 ml of a 1Msolution (0.9 mmol) of diethylaluminum chloride (DEAC), AlCl(C₂ H₅)₂ !,in hexanes was added to the CrEH₃ /PyH solution to form a CrEH₃/PyH/DEAC solution. A 0.65 ml aliquot of the CrEH₃ /PyH/DEAC solutionand 0.9 ml of a 1.1M solution (0.99 mmol) of TEA in heptane were addedto the autoclave reactor. The results are summarized below in TableXXIII.

Run 1005

The procedure described in Run 1001 was followed except 0.9 ml of a 1Msolution (0.9 mmol) of DEAC in hexanes was added to the CrEH₃ /PyHsolution and the resultant CrEH₃ /PyH/DEAC solution was aged for 1 dayat ambient temperature and pressure, under dry nitrogen. A 0.65 mlaliquot of the aged CrEH₃ /PyH/DEAC solution+0.9 ml of a 1.1M solution(0.99 mmol) of TEA in heptane were added to the autoclave reactor. Theresults are summarized below in Table XXIII.

Run 1006

The procedure described in Run 1001 was followed except a solution wasprepared using 0.13 ml pyrrole. Additionally, 1.0 ml of a 0.1M solution(0.1 mmol) of DEAC in hexanes was added along with the TEA to thereactor. A 0.9 ml aliquot of the CrEH₃ /PyH solution was used. Theresults are summarized below in Table XXIII.

Run 1007

The procedure described in Run 1003 was followed except 3 ml of a 1.9Msolution (5.7mmol) of TEA in toluene was used and toluene wassubstituted for the cyclohexane diluent in the formation of the CrEH₃/PyH/TEA solution. Thus, an excess of toluene was present inthe reactor.A 0.9 ml aliquot of the CrEH₃ /PyH/TEA solution was used. The resultsare summarized below in Table XXIII.

Run 1008

The procedure described in Run 1002 was followed except 0.10 g of achromium (III) pyrrolide (CrPy₃), Cr(C₄ H₄ N)₃ ClNa(C₄ H₁₀ O₂)₃ ! (0.17mmol) was substituted for CrEH₃, and a solution was prepared using 0.04ml (0.52 mmol) PyH and 3.5 ml of a 1.1M TEA (3.85 mmol) in heptanes. Thefinal solution volume was about 5 ml. A 1.0 ml aliquot of the CrPy₃/PyH/TEA solution was used. The results are summarized below in TableXXIII.

Run 1009

The procedure described in Run 1008 was followed except 1.8 ml of a 1.9MTEA solution (3.42 mmol) in toluene was used, and toluene wassubstituted for cyclohexane in the formation of the CrPy₃ /PyH/TEAsolution. Thus, an excess of toluene was present in the reactor. A 1.4ml aliquot of the CrPy₃ /PyH/TEA solution was used. The results aresummarized below in Table XXIII.

Run 1010

The procedure described in Run 1008 was followed except no neat PyH wasadded during the preparation of a CrPy₃ /TEA solution. A 1.4 ml aliquotof the CrPy₃ /TEA solution, in cyclohexane, was used. The results aresummarized below in Table XXIII.

Run 1011

The procedure described in Run 1009 was followed except no neat PyH wasadded during the preparation of a CrPy₃ /TEA solution. A 1.4 ml aliquotof the CrPy₃ /TEA solution, in toluene, was used. Thus, an excess oftoluene was present in the reactor. The results are summarized below inTable XXIII.

                                      TABLE XXIII                                 __________________________________________________________________________    Homogeneous Catalyst Systems                                                  mg Cr    Activity                                                                            Total       Liquid Product Distribution,                       (Elemental)                                                                            (g product/                                                                         Product                                                                           Wt. %                                                                             Wt. %                                                                             Weight Percent                                     Run                                                                              Charged                                                                             g Cr/Hr                                                                             Yield, g                                                                          Liquid                                                                            Solid                                                                             C.sub.4 ═                                                                    1-C.sub.6 ═                                                                   C.sub.6 ═                                                                    C.sub.8 ═                                                                    C.sub.10 ═                                                                    C.sub.12 ═                                                                    C.sub.14 ═                __________________________________________________________________________    1001                                                                             1.6   11,000                                                                              8.8 94  6   2  --  89.sup.a                                                                         2  6   <1  <1                            1002                                                                              0.96 8,800 4.2 88  12  1  87  5  2  4   <1  <1                            1003                                                                             2.6   9,800 12.8                                                                              64  36  2  81  4  4  5    1   1                            1004                                                                             1.1   15,000                                                                              8.5 98  2   <1 --  92.sup.a                                                                         1  6   <1  <1                            1005                                                                             1.1   26,000                                                                              14.9                                                                              98  2   <1 88  4  6  <1  <1  <1                            1006                                                                             1.5   12,000                                                                              9.0 98  2   <1 --  97.sup.a                                                                         1  2   <1  <1                            1007                                                                             2.6   3,500 4.6 50  50  2  86  4  3  3   <1  <1                            1008                                                                             2.5   8,300 10.5                                                                              >99 <1  1  83  5  <1 8   <1   1                            1009                                                                             2.5   4,100 5.2 99  1   1  88  4  1  6   <1  <1                            1010                                                                             2.5   7,100 8.9 97  3   <1 82  6  1  8   <1   1                            1011                                                                             2.5   3,300 4.2 98  2   <1 89  4  1  5   <1  <1                            __________________________________________________________________________     .sup.a Total hexenes.                                                    

EXAMPLE XI

It should be noted that the results in Table XXIII, from Example X, andthe results in Table XXIV, from Example XI, are not directly comparable,due to reactions conducted in different reactors, under differentconditions by the use of different ethylene and cyclohexane feedstocks,as well as different diluents. However, direct comparisons within eachExample can be made.

Run 2001

0.30 g (0.62 mmol) of chromium (III) 2-ethylhexanoate (CrEH₃) (10.15 wt% Cr) was combined with 0.12 ml (1.73 mmole) of neat pyrrole (PyH) in 10ml of toluene. 2.8 ml of 1.9M triethylaluminum (TEA) solution (5.32mmol) in toluene was added, and the CrEH₃ /PyH/TEA solution was stirredfor 30 minutes under dry nitrogen, at ambient temperature and pressure.The dark brown CrEH₃ /PyH/TEA solution was filtered and excess toluenewas removed by vacuum stripping, which resulted in 1.0 ml of a darkbrown oil, used as catalyst system. Under a counterflow of ethylene, 0.5ml (0.15 g CrEH₃ ; 15.2 mg Cr) of the catalyst system and 4.0 ml ofnonane (reactor internal standard) were added to a 2 liter autoclavereactor at 80° C., which contained 1.2 liters of cyclohexane. Thereactor was then pressurized with ethylene to 550 psig, and the reactionwas run for 30 minutes, with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2002

The procedure described in Run 2001 was followed except diethylaluminumchloride was added in addition to the CrEH₃ /PyH/TEA solution.

0.53 g (1.10 mmol) of CrEH₃ (10.15 wt. % Cr) was combined with 0.52 ml(7.5 mmole) of neat PyH in 15 ml of toluene and stirred for 5 min. 9.0ml of a 1.9M TEA solution (17.1 mmol) in toluene was added, and theCrEH₃ /PyH/TEA solution was stirred overnight under dry nitrogen atambient temperature and pressure. Excess toluene was removed from theresultant dark brown solution via vacuum stripping, which resulted in2.5 ml of a dark brown oil. 0.5 ml (10.8 mg; 0.21 mmole Cr) of the darkbrown oil was combined with 1.0 ml of a 0.87M (0.87 mmol)diethylaluminum chloride (DEAC) solution in nonane, and the CrEH₃/PyH/TEA/DEAC solution was stirred overnight under dry nitrogen, atambient temperature and pressure. The resultant product was used as thecatalyst system. Under a counterflow of ethylene, 1.3 ml (9.4 mg Cr;0.18 mmole Cr) of the catalyst system and 4.0 ml of nonane (reactorinternal standard) were charged directly to 2 a liter reactor at 80° C.,which contained 1.2 liters of cyclohexane. The reactor was thenpressurized with ethylene to 550 psig, and the reaction was run for 30minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2003

0.33 g (0.68 mmol) of CrEH₃ (10.15 wt. % Cr) was combined with 0.13 ml(1.87 mmole) of neat PyH in 10 ml of toluene and stirred 5 min. 1.9 mlof a 1M (1.9 mmol) DEAC solution in hexanes was added and the CrEH₃/PyH/DEAC solution was stirred for 30 minutes under dry nitrogen, atambient temperature and pressure, which resulted in a light yellow/green solution. 5.1 ml of a 1.9M (9.7 mmol) diethylaluminum chloride(DEAC) solution in toluene was added, and the CrEH₃ /PyH/DEAC/TEAsolution was stirred for 0.5 hr, which resulted in a dark yellow/brownsolution. Excess toluene and hexane was removed from the darkyellow/brown CrEH₃ /PyH/DEAC/TEA solution via vacuum stripping, with adark yellow/brown oil remaining. The yellow/brown oil was dissolved andbrought to a total volume in 25 ml of cyclohexane and used as a catalystsystem (1.32 mg Cr/ml). Under a counterflow of ethylene, 7.0 ml (9.2 mgCr; 0.178 mmole Cr) of the catalyst system and 4.0 ml of nonane (reactorinternal standard) were charged directly to a 2 liter reactor at 80° C.,which contained 1.2 liters of cyclohexane. The reactor was thenpressurized with ethylene to 550 psig and the reaction was run for 30minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2004

The procedure described in Run 2002 was followed, except the CrEH₃/PyH/TEA/DEAC solution was diluted with cyclohexane prior to charging tothe reactor, and dihydrogen gas (H₂) (50 psig) was added to the reactorprior to pressurizing the reactor with ethylene.

0.30 g (0.62 mmol) of CrEH₃ (10.15% Cr) was combined with 0.12 ml (1.73mmole) of neat PyH in 10 ml of toluene. 1.7 ml of a 1M (1.7 mmol) DEACsolution in hexanes was added and the CrEH/PyH/DEAC solution was stirredfor 5 minutes under dry nitrogen, at ambient temperature and pressure.1.8 ml of a 1.9M (3.42 mmol) TEA solution in toluene was added and theCrEH₃ /PyH/DEAC/TEA solution was stirred for 30 minutes under drynitrogen, at ambient temperature and pressure. The resultant dark brownsolution was filtered and excess toluene and hexanes were removed viavacuum stripping, which resulted in 0.8 ml of a dark yellow/brown oiland was used as a catalyst system. Under a counterflow of ethylene, 0.4ml (15.2 mg Cr; 0.29 mmole Cr) of the catalyst system and 4.0 ml ofnonane (reactor internal standard) were charged directly to the 2 literreactor at 80° C., which contained 1.2 liters of cyclohexane. 50 psig ofdihydrogen (H₂) gas was charged to the reactor, followed bypressurization with ethylene to 550 psig. The reaction was run for 30minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2005

In a 500 ml Schlenk flask 1.98 g (3.4 mmol) of CrPy₃ (11.1 wt. % Cr) wascombined with 40 ml of toluene and 54 ml of a 1.9M (102.6 mmol) TEAsolution in toluene. The resulting dark brown reaction mixture wasstirred for 1 hour under dry nitrogen, at ambient temperature andpressure. Excess toluene was removed via vacuum stripping, whichresulted in 13 ml of a dark yellow/brown oil and a small quantity of alight-colored precipitate. The dark yellow/brown oil was separated,collected by syringe from the precipitate, and used as the catalystsystem. 2.0 ml of the catalyst system was diluted with 27 ml ofcyclohexane and aged for 3 days under dry nitrogen, at ambienttemperature and pressure before using.

Under a counterflow of ethylene, 8.0 ml (9.3 mg; 0.18 mmole Cr) of thecatalyst system/cyclohexane solution and 4.0 ml of nonane (reactorinternal standard) were charged directly to a 2 liter autoclave reactorat 80° C., which contained 1.2 liters of cyclohexane. The reactor wasthen pressurized with ethylene to 550 psig and the reaction was run for30 minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2006

The procedure described in Run 2005 was followed except less reactantswere used and less aging time was used.

In a 500 ml Schlenk flask 0.25 g (0.432 mmol) of CrPy₃ (11.1 wt. % Cr)was combined with 10 ml of toluene and 3.4 ml of a 1.9M (6.46 mmol) TEAsolution in toluene. The resulting dark brown reaction mixture wasstirred for 30 minutes under dry nitrogen, at ambient temperature andpressure. Excess toluene was removed via vacuum stripping, whichresulted in a dark brown oil. All of the dark brown oil was diluted to atotal volume of 25 ml with cyclohexane, resulting in a solutioncontaining 1.11 mg Cr/ml, which was used as the catalyst system.

Under a counterflow of ethylene, 8.0 ml (8.88 mg; 0.171 mmole Cr) of thecatalyst system/cyclohexane solution and 4.0 ml of nonane (reactorinternal standard) were charged directly to a 2 liter autoclave reactorat 80° C., which contained 1.2 liters of cyclohexane. The reactor wasthen pressurized with ethylene to 550 psig and the reaction was run for30 minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2007

The procedure described in Run 2005 was followed except excess toluenewas present in the trimerization reactor.

In a 500 ml Schlenk flask 1.98 g (3.4 mmol) of CrPy₃ (11.1 wt. % Cr) wascombined with 40 ml of toluene and 54 ml of a 1.9M (102.6 mmol) TEAsolution in toluene. The resulting dark brown reaction mixture wasstirred for 1 hour under dry nitrogen, at ambient temperature andpressure. Excess toluene was removed via vacuum stripping, whichresulted in 13 ml of a dark yellow/brown oil and a small quantity of alight-colored precipitate. The dark yellow/brown oil was separated,collected by syringe from the precipitate, and used as the catalystsystem. 2.0 ml of the catalyst system was diluted with 27 ml ofcyclohexane and aged for 3 days under dry nitrogen, at ambienttemperature and pressure before using.

Under a counterflow of ethylene, 0.5 ml (8.5 mg; 0.163 mmole Cr) of thecatalyst system/cyclohexane solution, 4.5 ml of toluene, and 4.0 ml ofnonane (reactor internal standard) were charged directly to a 2 literautoclave reactor at 80° C., which contained 1.2 liters of cyclohexane.The reactor was then pressurized with ethylene to 550 psig and thereaction was run for 30 minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2008

0.28 g (0.802 mmol) of Cracac₃ was combined with 0.17 ml (2.45 mmol) ofneat pyrrole in 10 ml of toluene and stirred under dry nitrogen, atambient temperature and pressure for 5 minutes. Then, 6.3 ml of a 1.9M(12.0 mmol) TEA solution in toluene was added. The resulting dark brownreaction mixture was stirred for 30 minutes under dry nitrogen, atambient temperature and pressure. Excess toluene was removed via vacuumstripping, which resulted in a dark yellow/brown oil. All of the darkyellow/brown oil was diluted to a volume of 25 ml with cyclohexane,resulting in a solution containing 0.0112 g Cracac₃ /ml, which was usedas the catalyst system.

Under a counterflow of ethylene, 7.0 ml (15.2 mg; 0.293 mmole Cr) of thecatalyst system/cyclohexane solution and 4.0 ml of nonane (reactorinternal standard) were charged directly to a 2 liter autoclave reactorat 80° C., which contained 1.2 liters of cyclohexane. The reactor wasthen pressurized with ethylene to 550 psig and the reaction was run for30 minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2009

The procedure described in Run 2008 was followed except chromium (III)naphthenate was the chromium source.

0.33 g (0.508 mmol) of CrNapth₃ (8.0 wt. % Cr) was combined with 0.12(1.73 mmol) of neat pyrrole in 10 ml of toluene and stirred under drynitrogen at ambient temperature and pressure for 5 minutes. Then, 4.6 mlof a 1.9M (8.74 mmol) TEA solution in toluene was added. The resultingdark brown reaction mixture was stirred for 30 minutes under drynitrogen, at ambient temperature and pressure. Excess toluene wasremoved via vacuum stripping, which resulted in a dark yellow/brown oil.All of the dark yellow/brown oil was diluted to a total volume of 25 mlwith cyclohexane, resulting in a solution containing 1.056 mg Cr/ml,which was used as the catalyst system.

Under a counterflow of ethylene, 7.0 ml (7.39 mg; 0.142 mmole Cr) of thecatalyst system/cyclohexane solution and 4.0 ml of nonane (reactorinternal standard) were charged directly to a 2 liter autoclave reactorat 80° C., which contained 1.2 liters of cyclohexane. The reactor wasthen pressurized with ethylene to 550 psig and the reaction was run for30 minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2010

The procedure described in Run 2008 was followed except the chromium(III) chloride was the chromium source.

0.41 g (1.09 mmol) of CrCl₃ THF₃ was combined with 0.23 ml (3.32 mmol)of neat pyrrole in 10 ml of toluene and stirred under dry nitrogen, atambient temperature and pressure for 5 minutes. Then 8.6 ml of a 1.9M(16.3 mmol) TEA solution in toluene was added. The resulting dark brownreaction mixture was stirred for 30 minutes under dry nitrogen, atambient temperature and pressure. Excess toluene was removed via vacuumstripping, which resulted in a dark yellow/brown oil. 7.5 ml of nonanewas added to the dark yellow/brown oil and the resultant solution wasdiluted to a total volume of 25 ml with cyclohexane, resulting in asolution containing 0.0164 g CrCl₃ THF₃ /ml. The solution was filteredand the filtrate was used as the catalyst system.

Under a counterflow of ethylene, 5.0 ml (11.38 mg; 0.219 mmole Cr) ofthe catalyst system/cyclohexane/nonane solution and 2.5 ml of nonane(reactor internal standard) were charged directly to a 2 liter autoclavereactor at 80° C., which contained 1.2 liters of cyclohexane. Thereactor was then pressurized with ethylene to 550 psig and the reactionwas run for 30 minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2011

The procedure described in Run 2005 was followed except excess hexenewas charged to the trimerization reactor.

In a 500 ml Schlenk flask, 1.98 g (3.4 mmol) of CrPy₃ (11.1 wt. % Cr)was combined with 40 ml of toluene and 54 ml of a 1.9M (102.6 mmol) TEAsolution in toluene. The resulting dark brown reaction mixture wasstirred for 1 hour under dry nitrogen, at ambient temperature andpressure. Excess toluene was removed via vacuum stripping, whichresulted in 13 ml of a dark yellow/brown oil and a small quantity of alight-colored precipitate. The dark yellow/brown oil was separated,collected by syringe from the precipitate, and used as the catalystsystem. 2.0 ml of the catalyst system was diluted with 27 ml ofcyclohexane and aged for 3 days under dry nitrogen, at ambienttemperature and pressure before using.

Under a counterflow of ethylene, 1.0 ml (16.9 mg; 0.325 mmole Cr) of thecatalyst system/cyclohexane solution, 55 ml of 1-hexene, and 4.0 ml ofnonane (reactor internal standard) were charged directly to a 2 literautoclave reactor at 80° C., which contained 1.2 liters of cyclohexane.The reactor was then pressurized with ethylene to 550 psig and thereaction was run for 30 minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

Run 2012

The procedure described in Run 2005 was followed except chromium (II)pyrrolide (Compound I) was the chromium source.

0.30 g (about 0.85 mmol) of Compound I (CrPy₁₀ THF₄) was combined with10 ml of toluene and 6.7 ml of a 1.9M (12.7 mmol) TEA solution intoluene. The resulting dark brown reaction mixture was stirred for 30minutes under dry nitrogen, at ambient temperature and pressure. Excesstoluene was removed via vacuum stripping, which resulted in a darkyellow/brown oil and a small quantity of a light-colored precipitate.The dark yellow/brown oil was filtered and the filtrate was diluted to atotal volume of 25 ml with cyclohexane, resulting in a solutioncontaining 0.012 g Compound I (CrPy₁₀ THF₄), which was used as thecatalyst system.

Under a counterflow of ethylene, 7.0 ml of the catalystsystem/cyclohexane solution and 4.0 ml of nonane (reactor internalstandard) were charged directly to a 2 liter autoclave reactor at 80°C., which contained 1.2 liters of cyclohexane. The reactor was thenpressurized with ethylene to 550 psig and the reaction was run for 30minutes with ethylene being fed on demand.

The results are summarized below in Table XXIV.

                                      TABLE XXIV                                  __________________________________________________________________________    Catalyst Systems With Solvent Removal                                                   Molar                                                               mg Cr     Ratio Activity                                                                            Total       Liquid Product Distribution                 (Elemental)                                                                             Cr:Py:                                                                              (g product/                                                                         Product                                                                           Wt. %                                                                             Wt. %                                                                             Weight Percent                              Run Charged                                                                             TEA:DEAC                                                                            g Cr/hr)                                                                            Yield, g                                                                          Liquid                                                                            Solid                                                                             C.sub.4 ═                                                                     1-C.sub.6 ═                                                                   C.sub.6 ═                                                                     C.sub.8 ═                                                                     C.sub.10 ═                                                                    C.sub.12 ═                                                                    C.sub.14            __________________________________________________________________________                                                              ═               2001                                                                              15.2  1:3:9:0                                                                             4,000 30.5                                                                              74  26   9  53  2   9   9    5   4                  2002                                                                               9.3  1:7:15.5:4                                                                          6,000 23.2                                                                              95  5   <1  88  4   2   3   <1  <1                  2003                                                                               9.2  1:3:15:3                                                                            8,300 38.5                                                                              88  12  <1  86  3   2   5   <1  <1                  2004                                                                              15.2  1:3:6:3                                                                             4,900 37.0                                                                              96  4   <1  91  2   2   3   <1  <1                  2005                                                                               7.5  1:3:30:0                                                                            10,600                                                                              40.0                                                                              98  2   <1  82  9   1   7   <1  <1                  2006                                                                               7.2  1:3:15:0                                                                            10,800                                                                              38.9                                                                              97  3   <1  81  5   3   7   <1   1                  2007                                                                               6.8  1:3:30:0                                                                            1,100  3.2                                                                              94  6   4   84  6   1   4   <1  <1                  2008                                                                              11.8  1:3:15:0                                                                            17,000                                                                              98.9                                                                              95  5   <1  84  5   1   6   <1  <1                  2009                                                                               7.4  1:3:15:0                                                                            15,700                                                                              57.8                                                                              72  28  <1  88  2   2   5   <1  <1                  2010                                                                              11.4  1:3:15:0                                                                            8,000 45.3                                                                              98  2   <1  88  4   1   5   <1  <1                  2011                                                                              13.7  1:30:0:0                                                                            4,600 31.3                                                                              --  --  <1  76  11  1   10  <1   1                  2012                                                                              10.0  1:2:18.5:0                                                                          8,800 44.1                                                                              99  1   <1  77  9   1   11  <1   1                  __________________________________________________________________________

EXAMPLE XII Run 3001

0.21 g (0.601 mmol) of Cracac₃ was combined with 0.12 ml (1.73 mmol) ofneat pyrrole and 15 ml of toluene. The resulting solution was stirredunder dry nitrogen, at ambient temperature and pressure for 5 minutes.Then, 6.0 ml of a 1.9M (11.4 mmol) TEA solution in toluene was added.The resulting dark brown reaction mixture was stirred for 5 minutesunder dry nitrogen, at ambient temperature and pressure. Then, 2.0 g ofan aluminophosphate support (0.4 P/Al molar ratio, activated at 700°C.), prepared in accordance with U.S. Pat. No. 4,364,855 (1982), hereinincorporated by reference, was added and the resulting slurry stirredfor a period of approximately 12 hours. The product was collected byfiltration, rinsed at least twice with 10 ml aliquots of toluene andpentane, until no color was observed in the filtrate and vacuum dried.The dried product was used as solid supported catalyst system.

A 2.1022 g aliquot of the solid catalyst system was added under acounterflow of ethylene to a 2 liter autoclave containing 1 liter ofisobutane. Prior to the catalyst charge, 0.25 ml of a 16.5 wt % TEAsolution in nonane was added to the reactor, in order to neutralize anyethylene feedstock poisons that might be present. The reactor was sealedand ethylene addition was stopped until the reactor temperature reachedthe desired run temperature, for example 90° C. The ethylene pressurewas then increased to a total reactor pressure of 550 psig. Ethylene wasfed on demand for a 30 minute run time. At the end of the run, a sampleof the liquid reaction product mixture was collected and analyzed viagas chromatography. The remaining reaction mixture was evaporated andthe amount of solid product was determined.

The results are summarized in Table XXV.

Run 3002

The procedure described in Run 3001 was followed except diethylaluminumchloride was added to the Cracac₃ /PyH solution along with the TEA priorto the aluminophosphate inorganic oxide addition.

0.21 g Cracac₃ (0.60 mmol) was weighed into a 30 ml screw-capped vial.0.12 ml of PyH (1.73 mmol) and 15 ml of toluene were added, and theresulting solution was capped and stirred for 5 minutes. Then, withcontinued stirring, 6 ml of a 1.9M (11.4 mmol) TEA solution in toluenewas added. After the Cracac₃ /PyH/TEA solution was stirred for 5minutes, 2.4 ml of a 1M (2.4 mmol) DEAC solution in hexanes was addedand the Cracac₃ /PyH/TEA/DEAC/toluene solution was stirred for 5minutes. 2.0 g of an aluminophosphate support (0.4 P/Al molar ratio,activated at 700° C.), prepared in accordance with U.S. Pat. No.4,364,855 (1982), herein incorporated by reference, was added and theresulting slurry stirred for a period of approximately 12 hours. Theproduct was collected by filtration and rinsed with at least two 10 mlaliquots of toluene and pentane, until no color was observed in thefiltrate, and vacuum dried. The dried product was used as a solid,supported catalyst system.

A 0.5048 g aliquot of the solid catalyst system was added under acounterflow of ethylene to a 2 liter autoclave containing 1 liter ofisobutane. Prior to the catalyst charge, 3.0 ml of a 1.6 wt % TEAsolution in nonane was added in order to neutralize any ethylenefeedstock poisons that might be present. The reactor was sealed andethylene addition stopped until the reactor temperature reached thedesired run temperature, for example 90° C. The ethylene pressure wasincreased to a total reactor pressure of 550 psig. Ethylene was then fedon demand for a 30 minutes run time. At the end of the run, a smallsample of the liquid reaction product mixture was collected and analyzedvia gas chromatography. The remaining reaction mixture was evaporatedand the amount of solid product determined. Ethylene consumption wasdetermined by a calibrated flow meter.

The results are summarized below in Table XXV.

Run 3003

The procedure described in Run 3002 was followed except CrEH₃ was thechromium source and no aromatic solvent was used during catalyst systempreparation. Also, a supported catalyst system was prepared in-situ inthe reactor.

A CrEH₃ /PyH solution was prepared by mixing 0.33 g (0.69 mmole) CrEH₃with 0.26 ml (3.75 mmole) PyH in 16 ml of pentane and aging for 4 daysunder dry nitrogen, at ambient temperature and pressure, prior to usage.0.49 g of an aluminophosphate support (0.9 P/Al molar ratio, activatedat 700° C.), prepared in accordance with U.S. Pat. No. 4,364,855 (1982),herein incorporated by reference, and 2.0 ml of a 1M (2.0 mmol) TEAsolution in hexanes were charged under a counterflow of ethylene to a 2liter autoclave reactor at ambient temperature. Then, 1 liter ofcyclohexane, 2.1 ml (4.32 mg; 0.083 mmole Cr) of the CrEH₃ /PyHsolution, and 50 psig dihydrogen gas (H₂) were charged to the reactor.

The results are summarized below in Table XXV.

                                      TABLE XXV                                   __________________________________________________________________________    Grams  Molar Activity                                                         Catalyst                                                                             Ratio (g prod/g                                                                          Total       Liquid Product Distribution,                    System Cr:Py:                                                                              catalyst/                                                                          Product                                                                           Wt. %                                                                             Wt. %                                                                             Weight Percent                                  Run                                                                              Charged                                                                           TEA:DEAC                                                                            hr)  Yield, g                                                                          Liquid                                                                            Solid                                                                             C.sub.4 ═                                                                    1-C.sub.6 ═                                                                   C.sub.6 ═                                                                    C.sub.8 ═                                                                    C.sub.10 ═                                                                    C.sub.12 ═                                                                    C.sub.14 ═             __________________________________________________________________________    3001                                                                             2.1022                                                                            --    210  223 82  18  1  76  7  2  11  1   2                          3002                                                                             0.5048                                                                            1:3:19:4                                                                            340   87 99   1  1  82  7  1   8  <1  1                          3003                                                                             0.0426.sup.a                                                                      1:5.5:22.6:0                                                                        450  224 88  12  6  61  6  5  13  2   3                          __________________________________________________________________________     .sup.a Grams of only Cr(EH).sub.3 charged; mass of catalyst system            components are excluded.                                                 

EXAMPLE XIII Run 4001

3.5 g (10 mmol) Cracac₃ was weighed into a 100 ml pressure tube. A stirbar was placed in the tube and the tube was capped with a self sealingcrown cap. 40 ml toluene and 2.1 ml (30 mmol) PyH were added viasyringe. 12 ml of a 2.5M (30.0 mmol) n-butyl lithium solution in hexaneswas slowly added. A precipitate was formed, collected, and washed withone 10 ml aliquot of toluene and two 10 ml aliquots of cyclohexane,until no color was observed in the wash solution. A total of 5.59 gsolid was obtained. 0.5 ml of a 1.1M (0.55 mmol) TEA solution in heptaneand a slurry of 38 mg of the solid and cyclohexane were used in areaction under the conditions described in Run 1001.

The results are summarized below in Table XXVI.

EXAMPLE 4002

The procedure described in Run 4001 was followed except the solidcatalyst component (88 mg collected) was prepared in a 25 ml pressuretube using 0.349 g (1 mmol) Cracac₃, 5 ml toluene, 0.14 ml (2 mmol) PyH,and 0.8 ml of a 2.5M (2.0 mmol) n-butyl lithium solution in hexane.

0.5 ml of a 1.1M (0.55 mmol) TEA solution in heptanes and a cyclohexaneslurry containing 16 mg of the solid were used in a reaction under theconditions described in Run 1001.

The results are summarized below in Table XXVI.

Run 4003

1.0 g of aluminophosphate support (0.4 P/Al molar ratio, activated 700°C.), prepared in accordance with U.S. Pat. No. 4,364,855 (1982), hereinincorporated by reference, and an 93 mg aliquot of the solid describedin Run 4001, were weighed into a 25 ml pressure tube. The tube wascapped. 5 ml toluene and 3 ml of a 1.9M (5.7 mmol) TEA solution intoluene were added to the tube via syringe. The resulting slurry wasagitated for one day. The solid was isolated and washed with 10 mlaliquots of toluene and cyclohexane until no color was observed in thewash solution.

0.5 ml of a 1.1M (0.55 mmol) TEA solution in heptanes and a cyclohexaneslurry containing 80 mg of the solid were used in a reaction under theconditions described in Run 1001.

The results are summarized below in Table XXVI.

Run 4004

0.7 g of aluminophosphate support (0.4 P/Al molar ratio, activated at700° C.), prepared in accordance with U.S. Pat. No. 4,364,855 (1982),herein incorporated by reference, and an aliquot (53 mg) of the soliddescribed in Run 402 were weighed into a 25 ml pressure tube. The tubewas capped. 3.5 ml toluene and 2 ml of a 1.9M (3.8 mmol) TEA solution intoluene were added to the tube via syringe. The resulting slurry wasagitated for one day. The solid was isolated and washed with 10 mlaliquots of toluene and cyclohexane until no color was observed in thewash solution.

0.5 ml of a 1.1M (0.55 mmol) TEA solution in heptane and a cyclohexaneslurry containing 78 mg of the solid were used in a reaction under theconditions as described in Run 1001.

The results are summarized below in Table XXIV.

                                      TABLE XXVI                                  __________________________________________________________________________    Lithium-Alkyls in Catalyst Preparation                                        Grams  Activity                                                                           Total       Liquid Product Distribution,                          Catalyst                                                                             (g prod/                                                                           Product                                                                           Wt. %                                                                             Wt. %                                                                             Weight Percent                                        Run                                                                              Charged                                                                           g Cat/hr)                                                                          Yield, g                                                                          Liquid                                                                            Solid                                                                             C.sub.4 ═                                                                    1-C.sub.6 ═                                                                   C.sub.6 ═                                                                    C.sub.8 ═                                                                    C.sub.10 ═                                                                    C.sub.12 ═                                                                    --C--.sub.14 ═               __________________________________________________________________________    4001                                                                             0.038                                                                              95  1.8 86  14  4  81  5  3  4   <1  <1                               4002                                                                             0.016                                                                             540  4.3 82  18  3  83  5  3  4   <1  <1                               4003                                                                             0.080                                                                             110  4.3 89  11  1  79  5  3  5    2   1                               4004                                                                             0.078                                                                             310  12.2                                                                              84  16  1  78  6  2  8    1   1                               __________________________________________________________________________

EXAMPLE XIV Run 5001

0.17 g chromium (III) 2,2,6,6-tetramethyl-3,5-heptanedionate(Cr(III)TMHD) (0.28 mmol) was weighed into a 25 ml pressure tube. Thetube was capped with a self sealing crown cap. 0.06 ml of pyrrole (0.89mmol) and 0.17 ml of neat (0.87 mmol) diisobutylaluminum chloride(DiBAlCl) were added via syringe to form a Cr(III)TMHD/DiBAlCl/Pysolution, which was diluted to a total volume of about 8 ml withcyclohexane. 0.25 ml of a 1.1M (0.28 mmol) TEA solution in heptane and0.75 ml of the Cr(III)TMHD/DiBAlCl/Py solution were added to a glassbottle containing 100 ml of cyclohexane and 10 g of butadiene. The glassbottle was placed in a controlled temperature bath at 70° C., at ambientpressure, and agitated for a period of 16 hours. After 16 hours, a smallsample of the liquid reaction product mixture was collected and analyzedvia gas chromatography. The remaining liquid reaction product mixturewas evaporated and the amount of solid product was determined.

The results are summarized below in Table XXVII.

Run 5002

The procedure described in Run 5001 was followed except no excess alkylaluminum compound was present in the reactor and the catalyst wasderived using the procedure described in Run 3001, as follows.

0.21 g (0.601 mmol) of Cracac₃ was combined with 0.12 ml (1.73 mmol) ofneat pyrrole and 15 ml of toluene. The resulting solution was stirredunder dry nitrogen, at ambient temperature and pressure for 5 minutes.Then, 6.0 ml of a 1.9M (11.4 mmol) TEA solution in toluene was added.The resulting dark brown reaction mixture was stirred for 5 minutesunder dry nitrogen, at ambient temperature and pressure. Then, 2.0 g ofan aluminophosphate support (0.4 P/Al molar ratio, activated at 700° C.)prepared in accordance with U.S. Pat. No. 4,364,855 (1982), hereinincorporated by reference, was added and the resulting slurry stirredfor a period of approximately 12 hours. The product was collected byfiltration, rinsed at least twice with 10 mL aliquots of toluene andpentane, until no color was observed in the filtrate and vacuum dried.The dried product was used as a solid, supported catalyst system.

A 0.28 g catalyst charge was used in the butadiene reaction.

The results are summarized below in Table XXVII.

                  TABLE XXVII                                                     ______________________________________                                        Butadiene Reaction                                                            % Butadiene                                                                   Conversion  Distribution of Products, Weight %                                Run   to Products                                                                             1,5-Cyclooctadiene                                                                          Other Liquids                                                                          Solid                                  ______________________________________                                        5001  97        91.9          0.3       7.8                                   5002  68        60.8          2.5      36.7                                   ______________________________________                                    

EXAMPLE XV

In the following Runs, all catalyst systems were prepared in a glovebox, under dry nitrogen at ambient temperature and pressure. Transitionmetal compounds were weighed and combined with three (3) equivalents,(0.062) ml, pyrrole; 2 ml cyclohexane, as a solvent; and 6 ml of a 1.1Msolution of triethylaluminum (TEA) in heptane. The resulting product wasshaken for times varing from 5 minutes to 16 hours.

All runs were carried out in a 1 liter autoclave reactor containing 300ml cyclohexane. 1.0 ml of the liquid catalyst systems were diluted incyclohexane and were added to the reactor under a counter-flow ofethylene (CP grade). The reactor was sealed and ethylene additionstopped until the reactor temperature reached a reaction temperature of80° C. The ethylene pressure was increased to a total reactor pressureof 550 psig. Ethylene was fed on demand for a 30 minute run time. Ifnecessary, heat was applied to maintain a reactor temperature of 80° C.

At the end of each run, a sample of the liquid reaction product mixturewas taken and analyzed via capillary gas chromatography, on a HP-5880gas chromatograph equipped with an FID detector and a 60 meter DB-1column, with a 0.25 mm ID and a 0.25μ film. The gas chromatograph wasramped from 40° C. to 275° C. at a rate of 10° C./min, with a 20 minutehold time. Cyclobexane was used as an internal standard. The remainingreaction product mixture was evaporated and the amount of solid productproduced was determined.

The results are given in Table XXVIII.

                                      TABLE XXVIII                                __________________________________________________________________________                  Cata-                                                                     Grams,                                                                            lyst     Activity,         Liquid                                         Metal                                                                             System                                                                             Grams                                                                             (g product/                                                                         Grams,                                                                            Weight                                                                            Weight                                                                            Product Distribution,                    Metal Com-                                                                              Appear-                                                                            Catalyst                                                                          g catalyst/                                                                         total                                                                             Percent                                                                           Percent                                                                           Weight Percent                       Run Compound                                                                            pound                                                                             ance Charged                                                                           hr.)  Prod.                                                                             Liquid                                                                            Solid                                                                             C.sub.4 ═                                                                     1C.sub.6 ═                                                                    C.sub.6 ═                                                                     C.sub.8 ═                                                                     C.sub.10             __________________________________________________________________________                                                             ═                6001                                                                              Ni(acac).sub.2                                                                      0.075                                                                             dark 0.0094                                                                            324   1.52                                                                              95.4                                                                               4.6                                                                               4  65  4   7   9                                  brown                                                                         solution                                                                      some                                                                          solids                                                          6002                                                                              Ni(napth).sub.2                                                                     0.285                                                                             dark 0.0356                                                                             8    0.14                                                                              29.5                                                                              70.5                                                                              74   0  0   4   0                                  brown                                                                         solution                                                        6003                                                                              Co(acac).sub.2                                                                      0.075                                                                             brown                                                                              0.0094                                                                            59    0.28                                                                              78.5                                                                              21.5                                                                              71  13  0   11  1                                  solution,                                                                     dark                                                                          solid                                                           6004                                                                              Mn(acac).sub.2                                                                      0.073                                                                             brown-                                                                             0.0091                                                                            18    0.08                                                                              27.7                                                                              72.3                                                                              54   0  0   6   0                                  green                                                                         solution                                                        6005                                                                              Mn(acac).sub.3                                                                      0.102                                                                             brown                                                                              0.0128                                                                            12    0.08                                                                              23.7                                                                              76.3                                                                              50   0  0   0   0                                  solution                                                        6006                                                                              Cu(acac).sub.2                                                                      0.076                                                                             dark 0.0095                                                                            97    0.46                                                                              89.2                                                                              10.8                                                                               5   0  0   0   0                                  green                                                                         solution                                                        6007                                                                              MoO.sub.2 (acac).sub.2                                                              0.095                                                                             green/                                                                             0.0119                                                                            16    0.10                                                                              47.7                                                                              52.3                                                                              41   0  0   34  5                                  red                                                                           solution                                                                      some                                                                          solid                                                           6008                                                                              TiO(acac).sub.2                                                                     0.075                                                                             --   0.0094                                                                            222   1.04                                                                              71.2                                                                              28.8                                                                              11  48  7   8   20                   6009                                                                              VO(acac).sub.2                                                                      0.077                                                                             --   0.0096                                                                            115   0.56                                                                              56.8                                                                              43.2                                                                              15  50  13  16  2                    6010                                                                              Zr(acac).sub.2                                                                      0.141                                                                             --   0.0176                                                                            29    0.26                                                                              26.8                                                                              73.2                                                                               0  27  0   44  4                    __________________________________________________________________________

The data in Table XXVIII show that other metal compounds can trimerize,oligomerize, and/or polymerize 1-olefins. Of these metal compounds,Ni(acac)₂, Run 6001, showed the best activity and selectivity towardtrimerization.

EXAMPLE XVI

In the following Example, Runs 7001-7005 demonstrate the effect ofhydrolyzing the metal alkyl prior to use and the effect of the presenceand absence of a pyrrole-containing compound. Runs 7006-7009 compared toRuns 7010-7013 demonstrate the effect of preparation of a catalystsystem in an unsaturated hydrocarbon.

Runs 7001-7005

In Runs 7001-7005, the molar ratio of elemental chromium to elementalaluminum to ligand (Cr:Al:L), the catalyst components added to thereactor are 1:30:10. In Runs 7001-7003, the chromium compound wasCr(EH)3 and the chromium compound in Runs 7004 and 7005 was Cr(Py)₃. Thealuminum compound was triisobutylaluminum (i-Al(Bu)₃) and was treated inthe following manner. To an approximately ten percent, by weight,solution of triisobutylaluminum in heptane was added 1.0 mole equivalentof distilled water, steadily, but in one batch, while cooling the flaskcontaining the solution with ice water to maintain a temperature ofabout 10 to about 20° C. The solution was stirred vigorously during andafter water addition and continued until no further gas evolution wasobserved. The ligand was dimethoxyethane (DME).

Runs 7001-7005 were carried out in a 2 liter autoclave reactor. Thechromium compound was dissolved in 400-500 ml anhydrous n-heptane andadded to the reactor, under a dry nitrogen purge. Then the appropriatevolume of a stirred, treated 0.31M solution of i-Al(Bu)₃ in heptane, asdescribed above, was added. Then, the appropriate volume of DME wasadded, along with 5 ml of nonane (reactor internal standard). Thereactor was sealed and brought to a temperature of 80° C. in Run 7001and 95° C. in Runs 7002-7005 and a pressure of 550 psig with ethylene.Ethylene was fed on demand for a run time of 25 minutes in Run 7001, 30minutes in Run 7002 and 45 minutes in Runs 7003-7005.

At the end of each run, a sample of the liquid reaction product mixturewas taken and analyzed via capillary gas chromatography, on a HP-5800gas chromatograph equipped with an FID detector and a 60 meter DB-1column, with a 0.25 mm ID and a 0.25 μ film. The gas chromatograph wasramped from 40° C. to 275° C. at a rate of 10° C./min, with a 20 minutehold time. The remaining reaction product mixture was evaporated and theamount of solid product produced was determined.

The catalyst systems used in Runs 7006-7013 were prepared according tothe following procedures. Catalyst systems in Runs 7006-7009 wereprepared in the presence of toluene, an unsaturated aromatichydrocarbon. Catalyst systems in Runs 7010-7013 were prepared in thepresence of 1-hexene, an unsaturated aliphatic hydrocarbon.

Run 7006

3.72 g of Na(DME)₂ ! CrCl(Py)₃ DME! was combined with 50 ml toluene.Slowly, 26.4 ml of neat (93%) TEA was added and stirred for 30 minutes.The slurry turned dark brown. Excess solvent was removed by vacuum,resulting in a dark yellowish/brown oil and solid. About 70 mlcyclohexane was added. The resultant product was filtered and thefiltrate was diluted to 200 ml with cyclohexane and 8.0 ml were chargedto the reactor. The product contained 1.67 mg Cr/ml.

Run 7007

0.35 g of chromium(III) ethylhexanoate (CrEH₃) was combined with about15 ml of toluene, forming a deep green solution. 0.22 ml of2,5-dimethylpyrrole (2,5-DMP) and 0.20 ml of 1-bromobutane were added.Slowly, 5.7 ml of 1.9M TEA solution in toluene was added and stirred for30 minutes to give a greenish, brown solution and a solid. Excesssolvent was removed by vacuum and the liquid was extracted into about 15ml cyclohexane. The resultant product was filtered and the filtrate wasdiluted to 25 ml with cyclohexane to form a golden colored solution, ofwhich 7.0 ml were charged to the reactor. The product contained 0.014 gCrEH₃ /ml.

Run 7008

The procedure described in Run 7007 was followed, except 0.22 g CrEH3and 0.13 ml of 2,5-DMP were used. Furthermore, 0.10 ml of GeCl₄ weresubstituted for the 1-bromobutane. 3.4 ml of 1.9M TEA solution intoluene was added to give a brown to brown/yellow solution and aprecipitate. The final product after filtration and dilution to 25 mlwith cyclohexane, was a bright gold-yellow color and contained 0.0088 gCrEH₃ /ml. 3.0 ml were charged to the reactor.

Run 7009

2.070 g of CrPy₃ Cl was added to 70 ml toluene and 62 ml of 1.9M TEAsolution in toluene, mixed and filtered. The filtrate volume was reducedto about 20 ml by a dynamic vacuum. The viscous brown solution wasfiltered again. Then, about 30 ml of pentane was added to the filtrate.After about one day, the solution was vacuum stripped of excess solvent.Then 38.1 g of alumino-phosphate (P/Al molar ratio of 0.9, activation at700° C.), prepared in accordance with U.S. Pat. No. 4,364,855 wereadded. The slurry was stirred about 30 hours. The solid was collected byfiltration and washed separately with toluene, cyclohexane and pentane.0.4388 g of the solid catalyst system were charged to the reactor.

Run 7010

0.21 g of Na(DME)₂ ! CrCl(Py)₃ DME! was combined with about 15 ml1-hexene. Slowly, 0.75 ml of neat (93%) TEA was added, forming a brownsolution and a sticky-looking precipitate, and stirred for 30 minutes.Excess solvent was removed by vacuum. The residue was extracted intoabout 15 ml cyclohexane, filtered and the filtrate was diluted to 25 mlwith cyclohexane. 8.0 ml (0.067 g) were charged to the reactor.

Run 7011

The procedure described in Run 7010 was followed, except the finalcatalyst system, in cyclohexane, was aged for about 24 hours prior touse. 8.0 ml (0.067 g) were charged to the reactor.

Run 7012

0.26 g of CrEH₃ was dissolved in about 15 ml 1-hexene. 0.15 ml of2,5-DMP and 0.13 ml of 1-bromobutane were added. Slowly, 1.0 ml of neat(93%) TEA was added and stirred for 30 minutes. Excess solvent wasremoved by vacuum and the liquid was extracted into about 15 mlcyclohexane. The resultant product was filtered and the filtrate wasdiluted to 25 ml with cyclohexane. 7.0 ml were charged to the reactor.

Run 7013

0.21 g Na(DME)₂ ! CrCl(Py)₃ DME! was combined with about 15 ml 1-hexene.Slowly, 1.0 ml of neat (93%) TEA was added, forming a dark brownsolution and precipitate, and stirred for about 1 hour. The solution wasdecanted off and added to 1.5 g of aluminophosphate (P/Al molar ratio of0.4, activation at 700° C.), prepared in accordance with U.S. Pat. No.4,364,855, were added.

The supported catalyst system was collected by filtration, washed with1-hexene and dried under a nitrogen purge. 0.6328 g of the solidcatalyst system were charged to the reactor.

Runs 7006-7013 were carried out in a 1.2 liter autoclave reactor,containing cyclohexane. The heterogeneous, dried, supported catalystsystems (Runs 7009 and 7013) were slurried in cyclohexane to facilitateaddition to the polymerization reactor, and were added to thepolymerization reactor under a counter-flow of ethylene (CP grade). Thehomogeneous, liquid, unsupported catalyst systems (Runs 7006-7008 and7010-7012) were diluted in cylcohexane and were added to thepolymerization reactor under a counter-flow of ethylene (CP grade). Thereactor was sealed and ethylene addition stopped until the reactortemperature reached a reaction temperature of 80° C. The ethylenepressure was increased to a total reactor pressure of 550 psig. Ethylenewas then fed on demand for a 30 minute run time. At the end of the run,a sample of the liquid reaction product mixture was taken and analyzedvia capillary gas chromatography, on a HP-5880 gas chromatographequipped with a FID detector. The column was a 60 meter DB-1 column witha 0.25 mm ID and a 0.²⁵ μ film. The gas chromatograph was ramped from40° C. to 275° C. at a rate of 10° C./min, with a 20 minute hold time.The remaining reaction product mixture was evaporated and the amount ofsolid product produced was determined.

The results of the reactions are in Table XXIX, below.

                                      TABLE XXIX                                  __________________________________________________________________________                                           Liquid                                          mg Cr Activity,                                                                          Grams,                                                                             Weight                                                                            Weight                                                                            Molar Product Distribution,                  Catalyst (elemental)                                                                         g product/                                                                         Total                                                                              Percent                                                                           Percent                                                                           Ratios                                                                              Weight Percent                         Run System                                                                             Charged                                                                             g Cr/hr                                                                            Products                                                                           Liquid                                                                            Solid                                                                             Cr/N/Al/L.sup.(a)                                                                   C.sub.4 ═                                                                    1-C.sub.6 ═                                                                   C.sub.6 ═                                                                    C.sub.8 ═                                                                    C.sub.10 ═            __________________________________________________________________________    7001                                                                              Cr(EH).sub.3,                                                                      37.6  430  6.8  47  53  1/0/30/10                                                                           1  94  <1 4  <1                            DME, i-                                                                       Al(Bu).sub.3 /                                                                H.sub.2 O                                                                 7002.sup.(b)                                                                      Cr(EH).sub.3,                                                                      37.6  3,100                                                                              59.1 16  84  1/0/30/10                                                                           1  94  1  1  2                             DME, i-                                                                       Al(Bu).sub.3 /                                                                H.sub.2 O                                                                 7003                                                                              Cr(EH).sub.3,                                                                      13.2  4,000                                                                              39.7 64  36  1/0/30/10                                                                           1  95  <1 2  1                             DME, i-                                                                       Al(Bu).sub.3 /                                                                H.sub.2 O                                                                 7004                                                                              Cr(Py).sub.3.sup.(c)                                                               13.5  830  8.3  87  13  1/0/30/10                                                                           1  83  6  2  7                             DME, i-                                                                       Al(Bu).sub.3 /                                                                H.sub.2 O                                                                 7005                                                                              Cr(Py).sub.3.sup.(c)                                                               38.7  520  15.0 76  24  1/0/30/10                                                                           2  80  4  2  6                             DME, i-                                                                       Al(Bu).sub.3 /                                                                H.sub.2 O                                                                 7006                                                                              CrCl(Py).sub.3,                                                                    13.5  7,800                                                                              52.6 99.4                                                                              0.6 1/3/30/0                                                                            <1 82  10 1  7                             DME,                                                                          TEA                                                                       7007                                                                              Cr(EH).sub.3,                                                                      9.9   25,300                                                                             126.8                                                                              99.2                                                                              0.8 1/3/15/2.5                                                                          <1 92  2  <1 5                             25 DMP,                                                                       TEA,                                                                          n-BuBr                                                                    7008                                                                              Cr(EH).sub.3,                                                                      2.7   66,400                                                                             87.7 99.9                                                                              0.1 1/3/15/2.5                                                                          <1 98  <1 <1 <1                            25 DMP,                                                                       TEA,                                                                          GeCl.sub.4                                                                7009                                                                              CrCl(Py).sub.3,                                                                    0.397 g                                                                             69.sup.d                                                                           14.0 97.1                                                                              2.9 1/3/30/0                                                                            <1 87  7  1  3                             DME, Catalyst                                                                 0.9 P/Al                                                                  7010                                                                              CrCl(Py).sub.3,                                                                    6     5,200                                                                              16.3 96.3                                                                              3.7 1/3/15/0                                                                            16 55  2  12 8                             DME,                                                                          TEA                                                                       7011                                                                              CrCl(Py).sub.3,                                                                    6     5,070                                                                              15.9 96.2                                                                              3.8 1/3/15/0                                                                            15 55  2  12 8                             DME,                                                                          TEA                                                                       7012                                                                              Cr(EH).sub.3,                                                                      7.4   10,200                                                                             38.9 96.7                                                                              3.3 1/3/15/0                                                                            3  74  5  2  12                            2,5 DMP,                                                                      TEA,                                                                          n-BuBr                                                                    7013                                                                              CrCl(Py).sub.3,                                                                    0.6328 g                                                                            34.sup.d                                                                           19.0 56.8                                                                              43.2                                                                              1/3/15/2.5                                                                          9  45  3  10 10                            DME, Catalyst                                                                 TEA,                                                                          0.4 P/Al                                                                  __________________________________________________________________________     .sup.a) N is nitrogen containing compound, i.e., pyrrolecontaining            compound; L is ligand.                                                        .sup.b) Reactor plugged with solids.                                          .sup.c) CrCl(Py).sub.3 is equivalent to Cr(Py).sub.3,  Na(DME).sub.2 !         CrCl(Py).sub.3 DME!.                                                         .sup.d) Activity is in units of g product/g catalyst/hr.                 

The data in Table XXIX shows that the presence of water (Runs 7001-7005)is detrimental to the formation of liquids, such as for example,1-hexene. In fact, water in the reactor results in high solidsformation.

Runs 7006-7013 show that catalyst systems prepared in the presence ofany unsaturated hydrocarbon are effective toward trimerization. However,comparison of Runs 7006-7009, prepared in toluene, with Runs 7010-7013,prepared in 1-hexene, show that an unsaturated aromatic hydrocarbon isthe preferred catalyst system preparation medium.

EXAMPLE XVIII

The following Example, Runs 8001-8017, demonstrates the effect ofvarying the pyrrole compound, halogen, and metal additive used.

Catalyst systems used in Runs 8001-8017 were all prepared in the samegeneral procedure. In a typical preparation, chromium(III)2-ethylhexanoate was dissolved in toluene. Next, 3 equivalents of2,5-dimethylpyrrole (or hydrogen pyrrolide for Runs 8014-8017) was addedto the solution. The desired amount of halide additive (2 to 3 molarequivalents) was then added, followed by 15 molar equivalents oftriethylaluminum (TEA). The reaction mixture was stirred for 5-10minutes and toluene was removed under vacuum. The liquid residue wasdiluted to a total volume of 10 ml with cyclohexane and an aliquot wascharged to the reactor as the catalyst system.

The trimerization reaction runs were carried out in a 2-liter autoclavepolymerization reactor containing 1.2 liters of 85% cyclohexane as thereactor diluent. Catalyst system was charged to the reactor followed byaddition of cyclohexane. The reactor temperature was brought to 80° C.at which point ethylene was introduced. The pressure was maintained at550 psig with ethylene fed on demand. Each reaction was run for 30minutes before shutting off ethylene. Samples were taken at the end ofthe run and analyzed by gas chromatography, as described in otherexamples.

The results of the Runs and analyses are given in Table XXX.

                                      TABLE XXX                                   __________________________________________________________________________                                         Liquid Product                                       Molar   Activity,.sup.a                                                                    Total       Distribution, Weight                             mg Cr                                                                             Ratio   g liquid/g                                                                         Prod.                                                                             Wt. %                                                                             Wt. %                                                                             Percent                                  Run                                                                              Additive                                                                           Charged                                                                           Cr/Py/TEA/Add                                                                         Cr/hour                                                                            Grams                                                                             Liquid                                                                            Solid                                                                             C.sub.4 ═                                                                    1-C.sub.6 ═                                                                   C.sub.6 ═                                                                    C.sub.8 ═                                                                    C.sub.10 ═              __________________________________________________________________________    8001                                                                             None 13.7                                                                              1/3/15/0                                                                              4700 33.7                                                                              95  5   30 43  6  5  13                          8002                                                                             DEAC 14.2                                                                              1/3/15/3                                                                              16800                                                                              121.2                                                                             99  1   <1 86  3  1  8                           8003                                                                             DEAB 6.6 1/3/15/3                                                                              1800 61.5                                                                              98  2   <1 93  2  <1 4                           8004                                                                             DEA1-I                                                                             13.7                                                                              1/3/15/3                                                                               630 5.0 86  14   4 72  8  2  12                          8005                                                                             n-BuCl                                                                             6.8 1/3/15/3                                                                              6300 21.9                                                                              98  2   18 52  7  3  16                          8006                                                                             n-BuBr                                                                             6.9 1/3/15/2.5                                                                            27500                                                                              95.0                                                                              >99 <1  <1 91  2  <1 5                           8007                                                                             n-BuBr                                                                             9.9 1/3/15/2.5                                                                            25300                                                                              126.8                                                                             >99 <1  <1 92  2  <1 5                           8008                                                                             n-BuI                                                                              6.1 1/3/15/3                                                                              2000 7.2 85  15   4 71  7  2  14                          8009                                                                             Me.sub.3 SiCl                                                                      14.6                                                                              1/3/15/3                                                                              3600 26.9                                                                              97  3   16 57  6  4  14                          8010                                                                             Me.sub.3 SiBr                                                                      6.6 1/3/15/3                                                                              14000                                                                              46.6                                                                              >99 <1  <1 86  4  <1 8                           8011                                                                             GeCl.sub.4                                                                         6.6 1/3/15/2                                                                              55000                                                                              181.7                                                                             >99 <1  <1 96  <1 <1 3                           8012                                                                             GeCl.sub.4                                                                         2.7 1/3/15/2                                                                              66400                                                                              87.7                                                                              >99 <1  <1 98  <1 <1 <1                          8013                                                                             SnCl.sub.4                                                                         6.9 1/3/15/2                                                                              40600                                                                              140.4                                                                             >99 <1  <1 96  <1 <1 2                           8014                                                                             DEAC 10.8                                                                              1/3/15/2.5                                                                            6900 38.5                                                                              96  4   <1 87  4  2  5                           8015                                                                             DEAB 10.8                                                                              1/3/15/2.5                                                                            2600 14.3                                                                              97  3   <1 89  3  2  4                           8016                                                                             DEAL-I                                                                             10.8                                                                              1/3/15/2.5                                                                             70  0.4 44  56  19 60  6  3  4                           8017                                                                             GeCl.sub.4                                                                         10.8                                                                              1/3/15/2.5                                                                            3300 19.0                                                                              94  6   <1 95  2  1  2                           __________________________________________________________________________     .sup.a) Based on grams liquid product only.                              

The data in Table XXX show that the selectivity towards 1-hexeneincreases in the order I<Cl<Br. The bromine-containing additivesconsistently have the highest selectivity for the formation of 1-hexenecompared to the corresponding chloride or iodide additive. The increasedproduction of 1-hexene also means that less byproducts (C₄ =, C₈ =, andC₁₀ =) are being formed. The ratio of 1-hexene to internal hexenes alsotends to increase in the order I<Cl<Br. Thus, the use of halides leadsnot only to more product, but a cleaner trimer product as well. Theactivity of the catalyst system increases in the order I<<Cl, Br.However, the activity between Br and Cl analogues appear to beunpredictable. For some additives (SnX₄, and AlX₃ SiX₄) the Br is moreactive.

The data in Table XXX also show that the trend in selectivity to1-hexene and activity can be extended to catalysts containing otherpyrroles, as shown in Runs 8014-8017.

Overall, the best combination of activity and selectivity is obtainedusing GeCl₄ or SnCl₄ as the halide additives. However, it has been shownthat the selectivity towards 1-hexene is also affected by the ratio ofhalide additive to triethylaluminum, making it possible to obtain highselectivity from other halide additives.

EXAMPLE XVIII

In the following Example, Runs 9001-9004 demonstrate that excessunsaturated aromatic hydrocarbon can be detrimental to trimerizationand/or oligomerization. Thus, when a catalyst system is prepared in thepresence of an aromatic hydrocarbon, such as, for example, toluene,removal of excess aromatic hydrocarbon is preferred. The resultingliquid is then extracted or dissolved into a desired solvent, such as,for example cyclohexane or heptane. While not wishing to be bound bytheory, it is believed that an aromatic hydrocarbon can compete with amonomer to be trimerized and/or oligomerized, such as, for example,ethylene, for an active site of the catalyst system. Thus, it isbelieved that this competition can inhibit catalyst system activity.

The catalyst system used in Runs 9001-9004 was prepared using 1.35 g ofchromium(III) 2-ethylhexanoate dissolved in toluene. Next, 0.86 mL (3.2molar equivalents) of 2,5-dimethylpyrrole was added to the solution.Then 0.90 mL (3.2 molar equivalents) of n-butylbromide was added,followed by 7.60 mL (21 molar equivalents) of 93% triethylaluminum. Themixture mixture was stirred for 5-10 minutes and toluene was removedunder vacuum. The liquid residue was dissolved into 30 mL ofcyclohexane, filtered, and then diluted to a total volume of 50 mL withadditional cyclohexane. Four (4) mL of this solution was charged alongwith the desired amount of anhydrous, degassed toluene (0, 5, 10 or 15mL) to the reactor.

The trimerization reaction runs were carried out in a 2-liter autoclavepolymerization reactor containing 1.2 liters of 85% cyclohexane as thereactor diluent. Catalyst system was charged to the reactor followed byaddition of cyclohexane. The reactor temperature was brought to 80° C.at which point ethylene was introduced. The pressure was maintained at550 psig with ethylene fed on demand. Each reaction was run for 30minutes before shutting off ethylene. The total amount of ethyleneconsumed, i.e., fed, was measured.

The results of Runs 9001-9004 are given in Table XXXI.

                  TABLE XXXI                                                      ______________________________________                                        Effect of Aromatic Hydrocarbons                                               on Catalyst System Activity                                                                                 Ethylene                                                            Toluene   Consumed.sup.(b)                                       Toluene      Added,    After 30 mins,                                  Run    Added, ml    Volume %.sup.(a)                                                                        g                                               ______________________________________                                        9001    0           0.00      184                                             9002    5           0.42      160                                             9003   10           0.83      127                                             9004   15           1.25      109                                             ______________________________________                                         .sup.(a) Based on total volume of reactor diluent.                            .sup.(b) Not adjusted for solubility of ethylene in cyclohexane.         

The data in Table XXXI show that the presence of an aromatichydrocarbon, i.e., toluene, can result in a significant decrease in theactivity of the catalyst system, as measured by ethylene consumption.This decrease is proportional to the amount of aromatic hydrocarbonadded to the reactor.

EXAMPLE XIX

Ethylene-higher, alpha olefin copolymers were prepared in a continuous,particle form process by contacting ethylene with a polymerizationcatalyst system, prepared in accordance with U.S. Pat. No. 4,735,931,herein incorporated by reference, and a heterogeneous trimerizationand/or oligomerization catalyst system. Thetrimerization/oligomerization catalyst system was prepared by combiningin toluene 74 weight percent, based on the total weight of allcomponents, of aluminophosphate (P/Al molar ratio of 0.9, activated at700° C.), prepared in accordance with U.S. Pat. No. 4,364,855, hereinincorporated by reference; 22 weight percent neat TEA; 4 weight percent( Na(DME)₂ ! Cr(Py)₃ Cl(DME)!). The mixture was stirred for about 16hours, filtered, and rinsed with aliquots of toluene and pentane untilno color was observed in the filtrate. A light tan solid was recoveredand used as the catalyst system. At all times, preparation of theresultant and trimerization/oligomerization catalyst system were doneand kept under a dry, inert atmosphere at ambient temperature andpressure.

Copolymers were prepared by employing a full loop reactor, having avolume of 23 gallons (87 liters), with isobutane as a diluent. Thereactor was operated to have a residence time of 1.25 hours. The reactortemperature was about 93° C. and pressure was about 540 psi. At steadystate conditions, the isobutane feed rate was about 46 1/hr. Theethylene concentration in the reactor flash gas was between 9 and 10mole percent, based on the contents of the flash gas, including diluent.The results of two Runs in a continuous, particle form, loop reactor aregiven in Table XXXII. Run 1101 was modified by the addition ofdihydrogen (H₂) and TEA to the reactor. Run 1102 was modified by varyingthe trimerization catalyst system feed rates three times (Runs 1102a,1102b, and 1102c), and thus the ratios of each catalyst system.

For comparative purposes, the trimerization and/or oligomerizationcatalyst system, alone, was contacted with ethylene. The trimerizationrun was carried out in a 2-liter autoclave polymerization reactorcontaining 1.2 liters of isobutane as the reactor diluent. Trimerizationcatalyst system was charged to the reactor followed by addition ofisobutane. The reactor temperature was brought to 90° C. at which pointethylene was introduced. The pressure was maintained at 550 psig withethylene fed on demand. The reaction was run for 30 minutes beforeshutting off ethylene. Samples were taken at the end of the run andanalyzed by gas chromatography, as described in other examples.

Results of the trimerization Run are given in Table XXXIII.

                  TABLE XXXII                                                     ______________________________________                                               Weight Ratio                                                                  Trimerization:                                                                           TEA Added  H.sub.2                                                                             1-C.sub.6 ═                                                                     Polymer                                     Polymerization                                                                           to Reactor,                                                                              in Flash                                                                            in Flash                                                                            Density,                             Run    Catalysts  ppm.sup.(a)                                                                              Gas.sup.(b)                                                                         Gas.sup.(b)                                                                         g/cc.sup.(c)                         ______________________________________                                        1101   0.85:1     1          1     0.45- 0.948                                                                   0.5                                        1102a  0.85:1     None       None   0.63 0.944                                1102b  1.28:1     None       None  0.8   0.939                                1102c  1.62:1     None       None  1.0   0.937                                ______________________________________                                         .sup.(a) Based on isobutane diluent feed                                      .sup.(b) Mole percent, based on contents of flash gas, including diluent      .sup.(c) Determined on a compression molded sample, cooled at about           15° C. per hour, and conditioned for about 40 hours at room            temperature, in accordance with ASTM D1505 and ASTM D1928, condition C.  

                                      TABLE XXXIII                                __________________________________________________________________________    Weight Weight                                                                            Liquid Product Distribution,                                       Percent                                                                              Percent                                                                           Weight Percent                                                     Run                                                                              Liquid                                                                            Solid                                                                             C.sub.4 ═                                                                    1-C.sub.6 ═                                                                   C.sub.6 ═                                                                    C.sub.8 ═                                                                    C.sub.10 ═                                                                    C.sub.12 ═                                                                    C.sub.14 ═                                __________________________________________________________________________    1103                                                                             96  4   3  81  8  1  5   <1  <1                                            __________________________________________________________________________

The data in Table XXXII show that a polymerization and trimerizationcatalyst systems can be used in the same reactor to generatecomonomer(s) in-situ, and produce copolymers of ethylene and a higher,alpha olefin. Increasing the ratio of trimerization to polymerizationcatalyst system, results in more 1-hexene production and, therefore, alower polymer density.

EXAMPLE XX

All polymerization runs were carried out as described in Example VIII.

Density was determined in grams per cubic centimeter (g/cc) on acompression molded sample, cooled at about 15° C. per hour, andconditioned for about 40 hours at room temperature in accordance withASTM D1505 and ASTM D1928, condition C. The high load melt index (HLMI)was determined in accordance with ASTM D1238 at 190° C. with a 21,600gram weight. Melt index (MI) was determined according to ASTM D1238 at190° C. with a 2,160 gram weight.

Run 21: 0.100 g of Product V (prepared in the THF solvent), which washeated to 80° C. for 4 hours under nitrogen flush to remove residualTHF, was slurried with 15 ml toluene at ambient temperature. 7.0 ml of a1M TEA in hexanes solution was added and the solution stirred for 24hours. The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. An AlPO₄ (P/Al moleratio=0.4) (2.0 g) was added to the solution and stirred for 2 hours.The supported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice with pentane. 0.225 g of thiscatalyst was mixed with 0.89 g of a tergel-supported chromium catalystas two free-flowing powders. The tergel-supported chromium catalyst wasprepared in accordance with procedures in U.S. Pat. No. 3,887,494.0.2576 g of this catalyst mixture was charged directly to thepolymerization reactor. 3.0 ml of a 0.5% TEA in heptanes solution wascharged to the reactor after the catalyst charge, but before theisobutane (reactor solvent) charge, to purge feedstock poisons. Thereactor was pressurized to 550 psig with ethylene. After a 60.8 minuterun time, 190 g of polymer was produced. The polymer had a MI=6.5,HLMI=366.2, and a density equal to 0.9132 g/cc. The catalyst activitywas 730 g polymer/g catalyst/hr based on a 60.8 minute run time (runtemperature 90° C., 550 psig total pressure).

Run 22: 0.100 g of Product V (prepared in the THF solvent), which washeated to 80° C. for 4 hours under nitrogen flush to remove residualTHF, was slurried with 15 ml toluene at ambient temperature. 7.0 ml of a1M TEA in hexanes solution was added and the solution stirred for 24hours. The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. An AlPO₄ support (P/Almole ratio=0.4) (2.0 g) was added to the solution and stirred for 2hours. The supported catalyst was filtered from the solution as a brownsolid, rinsed twice with toluene, and then twice with pentane. 0.2314 gof this catalyst was mixed with 0.0184 g of a titanium-containingcatalyst as two free-flowing powders. The titanium-containing catalystwas prepared in accordance with procedures in U.S. Pat. No. 4,325,837and U.S. Pat. No. 4,326,988 wherein ethylaluminumdichloride was thealuminum alkyl used. 0.2385 g of this catalyst mixture was chargeddirectly to the polymerization reactor. 3.0 ml of a 0.5 percent TEA inheptanes solution was charged to the reactor after the catalyst charge,but before the isobutane (1 liter, to the reactor solvent) charge, topurge feedstock poisons. About 50 psig of dihydrogen (H₂) was thencharged to the reactor, followed by pressurizing to 550 psig withethylene. After a 31.0 minute run time, 82 g of polymer was produced.The polymer had a MI=0.011, HLMI=0.63, and a density equal to 0.9429g/cc. The catalyst activity was 670 g polymer/g catalyst/hr based on a31.0 run time (run temp. 90° C., 550 psig total pressure).

While this invention has been described in detail for the purpose ofillustration, it is not to be construed as limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

We claim:
 1. A process comprising polymerizing olefins in the presenceof a polymerization catalyst and a cocatalyst wherein said cocatalyst isprepared by a process comprising forming a mixture of:(a) a chromiumcompound selected from the group consisting of chromium salts having theformula CrX_(n) wherein "X" can be the same or different and is anorganic or inorganic radical and "n" is an integer from 1 to 6, andchromium metal; (b) a metal amide selected from the group consisting ofalkali metal amide salts, alkaline earth metal amide salts, and mixturesthereof; and (c) an ether; wherein said cocatalyst is a trimerization oroligomerization catalyst system and wherein said cocatalyst is differentfrom said polymerization catalyst system.
 2. A process according toclaim 1 wherein said polymerization catalyst is a supported chromiumcatalyst.
 3. A process according to claim 1 wherein said polymerizationcatalyst is a titanium-containing catalyst.
 4. A process according toclaim 1 wherein said cocatalyst comprises a chromium compound selectedfrom the group consisting of Cr₅ (C₄ H₄ N)₁₀ (C₄ H₈ O)₄ ; Cr(C₄ H₄ N)₄ ;Cr(C₄ H₄ N)₄ ! Na!₂.2(OC₄ H₈); Cr(C₄ H₄ N)₅ OC₄ H₈ !; Cr(C₄₄)₅ OC₄₈ !Na!₂.4(OC₄ H₈); and mixtures thereof.
 5. A process according to claim 1wherein said cocatalyst is supported on an inorganic oxide.
 6. A processaccording to claim 1 wherein said olefin has from 2 to about 30 carbonatoms per molecule.
 7. A process according to claim 6 wherein saidolefin is selected from the group consisting of ethylene, propylene,1-butene, 1-hexene, and mixtures thereof.
 8. A process according toclaim 7 wherein said olefin is predominantly ethylene.
 9. A processaccording to claim 1 wherein said polymerization is carried out at atemperature within the range of about 66° to about 110° C.
 10. A processaccording to claim 1 wherein hydrogen is present during saidpolymerization process.
 11. A process according to claim 1 wherein saidpolymerization process is a slurry polymerization process.
 12. A processaccording to claim 1 wherein a polymer is recovered.
 13. A processaccording to claim 1 wherein said olefin is ethylene and wherein apolymer is recovered which has a density within the range of about 0.9g/cc to about 0.96 g/cc.
 14. A process according to claim 1 wherein saidmetal amide has from about 1 to about 20 carbon atoms per molecule. 15.A process according to claim 1 wherein said metal amide is anunsaturated compound.
 16. A process according to claim 15 wherein saidmetal amide is an aromatic compound.
 17. A process according to claim 1wherein said metal amide has an amine ligand and wherein said amineligand is selected from the group consisting of pyrrolide ligands,derivatives of pyrrole ligands, and mixtures thereof.
 18. A processcomprising polymerizing olefins in the presence of a polymerizationcatalyst and a cocatalyst wherein said cocatalyst is prepared by aprocess comprising forming a mixture of and refluxing:(a) a chromiumcompound selected from the group consisting of chromium salts having theformula CrX_(n) wherein "X" can be the same or different and is anorganic or inorganic radical and "n" is an integer from 1 to 6, andchromium metal; (b) a metal amide selected from the group consisting ofalkali metal amide salts, alkaline earth metal amide salts, and mixturesthereof; and (c) an electron pair donor solvent; wherein said cocatalystis a trimerization or oligomerization catalyst system and wherein saidcocatalyst is different from said polymerization catalyst system.
 19. Aprocess according to claim 18 wherein said chromium compound is selectedfrom the group consisting of chromium acids, chromium halides, andmixtures thereof.
 20. A process according to claim 19 wherein saidchromium compound is a chromium halide selected from the groupconsisting of chromous chloride, chromic chloride, and mixtures thereof.21. A process according to claim 18 wherein said metal amide has fromabout 1 to about 20 carbon atoms per molecule.
 22. A process accordingto claim 18 wherein said metal amide is an unsaturated compound.
 23. Aprocess according to claim 22 wherein said metal amide is an aromaticcompound.
 24. A process according to claim 18 wherein said metal amidehas an amine ligand and wherein said amine ligand is selected from thegroup consisting of pyrrolide ligands, derivatives of pyrrole ligands,and mixtures thereof.
 25. A process according to claim 18 wherein saidelectron pair donor solvent has from about 2 to about 20 carbon atomsper molecule.
 26. A process according to claim 18 wherein said electronpair donor solvent is an aliphatic compound.
 27. A process according toclaim 18 wherein said metal amide is soluble in said electron pair donorsolvent.
 28. A process according to claim 18 wherein said electron pairdonor solvent is an ether and is selected from the group consisting oftetrahydrofuran, derivatives of tetrahydrofuran, dimethoxyethane,derivatives of dimethoxyethane, and mixtures thereof.
 29. A processaccording to claim 18 wherein said mixture is maintained in a liquidstate.
 30. A process according to claim 29 wherein said mixture ismaintained in a liquid state for a time in the range of about 1 minuteto about 1 week.